Improving of Mechanical and Shape-Memory Properties in Hyperbranched Epoxy Shape-Memory Polymers

NASA Astrophysics Data System (ADS)

Santiago, David; Fabregat-Sanjuan, Albert; Ferrando, Francesc; De la Flor, Silvia

2016-09-01

A series of shape-memory epoxy polymers were synthesized using an aliphatic amine and two different commercial hyperbranched poly(ethyleneimine)s with different molecular weights as crosslinking agents. Thermal, mechanical, and shape-memory properties in materials modified with different hyperbranched polymers were analyzed and compared in order to establish the effect of the structure and the molecular weight of the hyperbranched polymers used. The presence of hyperbranched polymers led to more heterogeneous networks, and the crosslinking densities of which increase as the hyperbranched polymer content increases. The transition temperatures can be tailored from 56 to 117 °C depending on the molecular weight and content of the hyperbranched polymer. The mechanical properties showed excellent values in all formulations at room temperature and, specially, at T_{{g}}^{{E^' with stress at break as high as 15 MPa and strain at break as high as 60 %. The shape-memory performances revealed recovery ratios around 95 %, fixity ratios around 97 %, and shape-recovery velocities as high as 22 %/min. The results obtained in this study reveal that hyperbranched polymers with different molecular weights can be used to enhance the thermal and mechanical properties of epoxy-based SMPs while keeping excellent shape-memory properties.

Guide wire extension for shape memory polymer occlusion removal devices

DOEpatents

Maitland, Duncan J [Pleasant Hill, CA; Small, IV, Ward; Hartman, Jonathan [Sacramento, CA

2009-11-03

A flexible extension for a shape memory polymer occlusion removal device. A shape memory polymer instrument is transported through a vessel via a catheter. A flexible elongated unit is operatively connected to the distal end of the shape memory polymer instrument to enhance maneuverability through tortuous paths en route to the occlusion.

Reversible Shape Memory Polymers and Composites: Synthesis, Modeling and Design

DTIC Science & Technology

2013-03-01

Polymer; and (iii) Development of a Shape Memory Assisted Self - Healing Polymer. Page 3 of 19 Mather/FA9550-09-1-0195 IV(i) Modeling and Model...0195 IV(iii) Development of a Shape Memory Assisted Self - Healing Polymer Erika D. Rodriguez, X. Luo, and P.T. Mather, “Linear and Crosslinked...Poly (ε- Caprolactone) Polymers for Shape Memory Assisted Self - Healing (SMASH),” ACS Applied Materials and Interfaces 3 152-161 (2011). Self

Reconfigurable photonic crystals enabled by pressure-responsive shape-memory polymers

PubMed Central

Fang, Yin; Ni, Yongliang; Leo, Sin-Yen; Taylor, Curtis; Basile, Vito; Jiang, Peng

2015-01-01

Smart shape-memory polymers can memorize and recover their permanent shape in response to an external stimulus (for example, heat). They have been extensively exploited for a wide spectrum of applications ranging from biomedical devices to aerospace morphing structures. However, most of the existing shape-memory polymers are thermoresponsive and their performance is hindered by heat-demanding programming and recovery steps. Although pressure is an easily adjustable process variable such as temperature, pressure-responsive shape-memory polymers are largely unexplored. Here we report a series of shape-memory polymers that enable unusual ‘cold' programming and instantaneous shape recovery triggered by applying a contact pressure at ambient conditions. Moreover, the interdisciplinary integration of scientific principles drawn from two disparate fields—the fast-growing photonic crystal and shape-memory polymer technologies—enables fabrication of reconfigurable photonic crystals and simultaneously provides a simple and sensitive optical technique for investigating the intriguing shape-memory effects at nanoscale. PMID:26074349

AC Electric Field Activated Shape Memory Polymer Composite

NASA Technical Reports Server (NTRS)

Kang, Jin Ho; Siochi, Emilie J.; Penner, Ronald K.; Turner, Travis L.

2011-01-01

Shape memory materials have drawn interest for applications like intelligent medical devices, deployable space structures and morphing structures. Compared to other shape memory materials like shape memory alloys (SMAs) or shape memory ceramics (SMCs), shape memory polymers (SMPs) have high elastic deformation that is amenable to tailored of mechanical properties, have lower density, and are easily processed. However, SMPs have low recovery stress and long response times. A new shape memory thermosetting polymer nanocomposite (LaRC-SMPC) was synthesized with conductive fillers to enhance its thermo-mechanical characteristics. A new composition of shape memory thermosetting polymer nanocomposite (LaRC-SMPC) was synthesized with conductive functionalized graphene sheets (FGS) to enhance its thermo-mechanical characteristics. The elastic modulus of LaRC-SMPC is approximately 2.7 GPa at room temperature and 4.3 MPa above its glass transition temperature. Conductive FGSs-doped LaRC-SMPC exhibited higher conductivity compared to pristine LaRC SMP. Applying an electric field at between 0.1 Hz and 1 kHz induced faster heating to activate the LaRC-SMPC s shape memory effect relative to applying DC electric field or AC electric field at frequencies exceeding1 kHz.

Fabrication and characterization of shape memory polymers at small-scales

NASA Astrophysics Data System (ADS)

Wornyo, Edem

The objective of this research is to thoroughly investigate the shape memory effect in polymers, characterize, and optimize these polymers for applications in information storage systems. Previous research effort in this field concentrated on shape memory metals for biomedical applications such as stents. Minimal work has been done on shape memory polymers; and the available work on shape memory polymers has not characterized the behaviors of this category of polymers fully. Copolymer shape memory materials based on diethylene glycol dimethacrylate (DEGDMA) crosslinker, and tert butyl acrylate (tBA) monomer are designed. The design encompasses a careful control of the backbone chemistry of the materials. Characterization methods such as dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC); and novel nanoscale techniques such as atomic force microscopy (AFM), and nanoindentation are applied to this system of materials. Designed experiments are conducted on the materials to optimize spin coating conditions for thin films. Furthermore, the recovery, a key for the use of these polymeric materials for information storage, is examined in detail with respect to temperature. In sum, the overarching objectives of the proposed research are to: (i) Design shape memory polymers based on polyethylene glycol dimethacrylate (PEGDMA) and diethylene glycol dimethacrylate (DEGDMA) crosslinkers, 2-hydroxyethyl methacrylate (HEMA) and tert-butyl acrylate monomer (tBA). (ii) Utilize dynamic mechanical analysis (DMA) to comprehend the thermomechanical properties of shape memory polymers based on DEGDMA and tBA. (iii) Utilize nanoindentation and atomic force microscopy (AFM) to understand the nanoscale behavior of these SMPs, and explore the strain storage and recovery of the polymers from a deformed state. (iv) Study spin coating conditions on thin film quality with designed experiments. (iv) Apply neural networks and genetic algorithms to optimize these systems.

Polymer therapeutics in surgery: the next frontier

PubMed Central

Conlan, R. Steven; Whitaker, Iain S.

2016-01-01

Abstract Polymer therapeutics is a successful branch of nanomedicine, which is now established in several facets of everyday practice. However, to our knowledge, no literature regarding the application of the underpinning principles, general safety, and potential of this versatile class to the perioperative patient has been published. This study provides an overview of polymer therapeutics applied to clinical surgery, including the evolution of this demand‐oriented scientific field, cutting‐edge concepts, its implications, and limitations, illustrated by products already in clinical use and promising ones in development. In particular, the effect of design of polymer therapeutics on biophysical and biochemical properties, the potential for targeted delivery, smart release, and safety are addressed. Emphasis is made on principles, giving examples in salient areas of demand in current surgical practice. Exposure of the practising surgeon to this versatile class is crucial to evaluate and maximise the benefits that this established field presents and to attract a new generation of clinician–scientists with the necessary knowledge mix to drive highly successful innovation. PMID:27588210

Memory operation mechanism of fullerene-containing polymer memory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakajima, Anri, E-mail: anakajima@hiroshima-u.ac.jp; Fujii, Daiki

2015-03-09

The memory operation mechanism in fullerene-containing nanocomposite gate insulators was investigated while varying the kind of fullerene in a polymer gate insulator. It was cleared what kind of traps and which positions in the nanocomposite the injected electrons or holes are stored in. The reason for the difference in the easiness of programming was clarified taking the role of the charging energy of an injected electron into account. The dependence of the carrier dynamics on the kind of fullerene molecule was investigated. A nonuniform distribution of injected carriers occurred after application of a large magnitude programming voltage due to themore » width distribution of the polystyrene barrier between adjacent fullerene molecules. Through the investigations, we demonstrated a nanocomposite gate with fullerene molecules having excellent retention characteristics and a programming capability. This will lead to the realization of practical organic memories with fullerene-containing polymer nanocomposites.« less

Release mechanism utilizing shape memory polymer material

DOEpatents

Lee, Abraham P.; Northrup, M. Allen; Ciarlo, Dino R.; Krulevitch, Peter A.; Benett, William J.

2000-01-01

Microfabricated therapeutic actuators are fabricated using a shape memory polymer (SMP), a polyurethane-based material that undergoes a phase transformation at a specified temperature (Tg). At a temperature above temperature Tg material is soft and can be easily reshaped into another configuration. As the temperature is lowered below temperature Tg the new shape is fixed and locked in as long as the material stays below temperature Tg. Upon reheating the material to a temperature above Tg, the material will return to its original shape. By the use of such SMP material, SMP microtubing can be used as a release actuator for the delivery of embolic coils through catheters into aneurysms, for example. The microtubing can be manufactured in various sizes and the phase change temperature Tg is determinate for an intended temperature target and intended use.

Functional polymers as therapeutic agents: concept to market place.

PubMed

Dhal, Pradeep K; Polomoscanik, Steven C; Avila, Louis Z; Holmes-Farley, S Randall; Miller, Robert J

2009-11-12

Biologically active synthetic polymers have received considerable scientific interest and attention in recent years for their potential as promising novel therapeutic agents to treat human diseases. Although a significant amount of research has been carried out involving polymer-linked drugs as targeted and sustained release drug delivery systems and prodrugs, examples on bioactive polymers that exhibit intrinsic therapeutic properties are relatively less. Several appealing characteristics of synthetic polymers including high molecular weight, molecular architecture, and controlled polydispersity can all be utilized to discover a new generation of therapies. For example, high molecular weight bioactive polymers can be restricted to gastrointestinal tract, where they can selectively recognize, bind, and remove target disease causing substances from the body. The appealing features of GI tract restriction and stability in biological environment render these polymeric drugs to be devoid of systemic toxicity that are generally associated with small molecule systemic drugs. The present article highlights recent developments in the rational design and synthesis of appropriate functional polymers that have resulted in a number of promising polymer based therapies and biomaterials, including some marketed products.

Residual stresses in injection molded shape memory polymer parts

NASA Astrophysics Data System (ADS)

Katmer, Sukran; Esen, Huseyin; Karatas, Cetin

2016-03-01

Shape memory polymers (SMPs) are materials which have shape memory effect (SME). SME is a property which has the ability to change shape when induced by a stimulator such as temperature, moisture, pH, electric current, magnetic field, light, etc. A process, known as programming, is applied to SMP parts in order to alter them from their permanent shape to their temporary shape. In this study we investigated effects of injection molding and programming processes on residual stresses in molded thermoplastic polyurethane shape memory polymer, experimentally. The residual stresses were measured by layer removal method. The study shows that injection molding and programming process conditions have significantly influence on residual stresses in molded shape memory polyurethane parts.

Thermal response of novel shape memory polymer-shape memory alloy hybrids

NASA Astrophysics Data System (ADS)

Rossiter, Jonathan; Takashima, Kazuto; Mukai, Toshiharu

2014-03-01

Shape memory polymers (SMP) and shape memory alloys (SMA) have both been proven important smart materials in their own fields. Shape memory polymers can be formed into complex three-dimensional structures and can undergo shape programming and large strain recovery. These are especially important for deployable structures including those for space applications and micro-structures such as stents. Shape memory alloys on the other hand are readily exploitable in a range of applications where simple, silent, light-weight and low-cost repeatable actuation is required. These include servos, valves and mobile robotic artificial muscles. Despite their differences, one important commonality between SMPs and SMAs is that they are both typically activated by thermal energy. Given this common characteristic it is important to consider how these two will behave when in close environmental proximity, and hence exposed to the same thermal stimulus, and when they are incorporated into a hybrid SMA-SMP structure. In this paper we propose and examine the operation of SMA-SMP hybrids. The relationship between the two temperatures Tg, the glass transition temperature of the polymer, and Ta, the nominal austenite to martensite transition temperature of the alloy is considered. We examine how the choice of these two temperatures affects the thermal response of the hybrid. Electrical stimulation of the SMA is also considered as a method not only of actuating the SMA but also of inducing heating in the surrounding polymer, with consequent effects on actuator behaviour. Likewise by varying the rate and degree of thermal stimulation of the SMA significantly different actuation and structural stiffness can be achieved. Novel SMP-SMA hybrid actuators and structures have many ready applications in deployable structures, robotics and tuneable engineering systems.

Electrochromic conductive polymer fuses for hybrid organic/inorganic semiconductor memories

NASA Astrophysics Data System (ADS)

Möller, Sven; Forrest, Stephen R.; Perlov, Craig; Jackson, Warren; Taussig, Carl

2003-12-01

We demonstrate a nonvolatile, write-once-read-many-times (WORM) memory device employing a hybrid organic/inorganic semiconductor architecture consisting of thin film p-i-n silicon diode on a stainless steel substrate integrated in series with a conductive polymer fuse. The nonlinearity of the silicon diodes enables a passive matrix memory architecture, while the conductive polyethylenedioxythiophene:polystyrene sulfonic acid polymer serves as a reliable switch with fuse-like behavior for data storage. The polymer can be switched at ˜2 μs, resulting in a permanent decrease of conductivity of the memory pixel by up to a factor of 103. The switching mechanism is primarily due to a current and thermally dependent redox reaction in the polymer, limited by the double injection of both holes and electrons. The switched device performance does not degrade after many thousand read cycles in ambient at room temperature. Our results suggest that low cost, organic/inorganic WORM memories are feasible for light weight, high density, robust, and fast archival storage applications.

Autobiographical Memory Disturbances in Depression: A Novel Therapeutic Target?

PubMed Central

Köhler, Cristiano A.; Carvalho, André F.; Alves, Gilberto S.; McIntyre, Roger S.; Hyphantis, Thomas N.; Cammarota, Martín

2015-01-01

Major depressive disorder (MDD) is characterized by a dysfunctional processing of autobiographical memories. We review the following core domains of deficit: systematic biases favoring materials of negative emotional valence; diminished access and response to positive memories; a recollection of overgeneral memories in detriment of specific autobiographical memories; and the role of ruminative processes and avoidance when dealing with autobiographical memories. Furthermore, we review evidence from functional neuroimaging studies of neural circuits activated by the recollection of autobiographical memories in both healthy and depressive individuals. Disruptions in autobiographical memories predispose and portend onset and maintenance of depression. Thus, we discuss emerging therapeutics that target memory difficulties in those with depression. We review strategies for this clinical domain, including memory specificity training, method-of-loci, memory rescripting, and real-time fMRI neurofeedback training of amygdala activity in depression. We propose that the manipulation of the reconsolidation of autobiographical memories in depression might represent a novel yet largely unexplored, domain-specific, therapeutic opportunity for depression treatment. PMID:26380121

Methods of Making and Using Shape Memory Polymer Composite Patches

NASA Technical Reports Server (NTRS)

Hood, Patrick J.

2011-01-01

A method of repairing a composite component having a damaged area including: laying a composite patch over the damaged area: activating the shape memory polymer resin to easily and quickly mold said patch to said damaged area; deactivating said shape memory polymer so that said composite patch retains the molded shape; and bonding said composite patch to said damaged part.

A polymer/semiconductor write-once read-many-times memory

NASA Astrophysics Data System (ADS)

Möller, Sven; Perlov, Craig; Jackson, Warren; Taussig, Carl; Forrest, Stephen R.

2003-11-01

Organic devices promise to revolutionize the extent of, and access to, electronics by providing extremely inexpensive, lightweight and capable ubiquitous components that are printed onto plastic, glass or metal foils. One key component of an electronic circuit that has thus far received surprisingly little attention is an organic electronic memory. Here we report an architecture for a write-once read-many-times (WORM) memory, based on the hybrid integration of an electrochromic polymer with a thin-film silicon diode deposited onto a flexible metal foil substrate. WORM memories are desirable for ultralow-cost permanent storage of digital images, eliminating the need for slow, bulky and expensive mechanical drives used in conventional magnetic and optical memories. Our results indicate that the hybrid organic/inorganic memory device is a reliable means for achieving rapid, large-scale archival data storage. The WORM memory pixel exploits a mechanism of current-controlled, thermally activated un-doping of a two-component electrochromic conducting polymer.

Memory as a new therapeutic target

PubMed Central

Nader, Karim; Hardt, Oliver; Lanius, Ruth

2013-01-01

This review aims to demonstrate how an understanding of the brain mechanisms involved in memory provides a basis for; (i) reconceptualizing some mental disorders; (ii) refining existing therapeutic tools; and (iii) designing new ones for targeting processes that maintain these disorders. First, some of the stages which a memory undergoes are defined, and the clinical relevance of an understanding of memory processing by the brain is discussed. This is followed by a brief review of some of the clinical studies that have targeted memory processes. Finally, some new insights provided by the field of neuroscience with implications for conceptualizing mental disorders are presented. PMID:24459414

Unconstrained Recovery Characterization of Shape-Memory Polymer Networks for Cardiovascular Applications

PubMed Central

Yakacki, Christopher M.; Shandas, Robin; Lanning, Craig; Rech, Bryan; Eckstein, Alex; Gall, Ken

2009-01-01

Shape-memory materials have been proposed in biomedical device design due to their ability to facilitate minimally invasive surgery and recover to a predetermined shape in-vivo. Use of the shape-memory effect in polymers is proposed for cardiovascular stent interventions to reduce the catheter size for delivery and offer highly controlled and tailored deployment at body temperature. Shape-memory polymer networks were synthesized via photopolymerization of tert-butyl acrylate and poly (ethylene glycol) dimethacrylate to provide precise control over the thermomechanical response of the system. The free recovery response of the polymer stents at body temperature was studied as a function of glass transition temperature (Tg), crosslink density, geometrical perforation, and deformation temperature, all of which can be independently controlled. Room temperature storage of the stents was shown to be highly dependent on Tg and crosslink density. The pressurized response of the stents is also demonstrated to depend on crosslink density. This polymer system exhibits a wide range of shape-memory and thermomechanical responses to adapt and meet specific needs of minimally invasive cardiovascular devices. PMID:17296222

Durability of carbon fiber reinforced shape memory polymer composites in space

NASA Astrophysics Data System (ADS)

Jang, Joon Hyeok; Hong, Seok Bin; Ahn, Yong San; Kim, Jin-Gyun; Nam, Yong-Youn; Lee, Geun Ho; Yu, Woong-Ryeol

2016-04-01

Shape memory polymer (SMP) is one of smart polymers which exhibit shape memory effect upon external stimuli. Recently, shape memory polymer composites (SMPCs) have been considered for space structure instead of shape memory alloys due to their deformability, lightweight and large recovery ratio, requiring characterization of their mechanical properties against harsh space environment and further prediction of the durability of SMPCs in space. As such, the durability of carbon fiber reinforced shape memory polymer composites (CF-SMPCs) was investigated using accelerated testing method based on short-term testing of CF-SMPCs in harsh condition. CF-SMPCs were prepared using woven carbon fabrics and a thermoset SMP via vacuum assisted resin transfer molding process. Bending tests with constant strain rate of CF-SMPCs were conducted using universal tensile machine (UTM) and Storage modulus test were conducted using dynamic mechanical thermal analysis (DMTA). Using the results, a master curve based on time-temperature superposition principle was then constructed, through which the mechanical properties of CF-SMPCs at harsh temperature were predicted. CF-SMPCs would be exposed to simulated space environments under ultra-violet radiations at various temperatures. The mechanical properties including flexural and tensile strength and shape memory properties of SMPCs would be measured using UTM before and after such exposures for comparison. Finally, the durability of SMPCs in space would be assessed by developing a degradation model of SMPC.

A Facile and General Approach to Recoverable High-Strain Multishape Shape Memory Polymers.

PubMed

Li, Xingjian; Pan, Yi; Zheng, Zhaohui; Ding, Xiaobin

2018-03-01

Fabricating a single polymer network with no need to design complex structures to achieve an ideal combination of tunable high-strain multiple-shape memory effects and highly recoverable shape memory property is a great challenge for the real applications of advanced shape memory devices. Here, a facile and general approach to recoverable high-strain multishape shape memory polymers is presented via a random copolymerization of acrylate monomers and a chain-extended multiblock copolymer crosslinker. As-prepared shape memory networks show a large width at the half-peak height of the glass transition, far wider than current classical multishape shape memory polymers. A combination of tunable high-strain multishape memory effect and as high as 1000% recoverable strain in a single chemical-crosslinking network can be obtained. To the best of our knowledge, this is the first thermosetting material with a combination of highly recoverable strain and tunable high-strain multiple-shape memory effects. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Resistive switching characteristics of polymer non-volatile memory devices in a scalable via-hole structure.

PubMed

Kim, Tae-Wook; Choi, Hyejung; Oh, Seung-Hwan; Jo, Minseok; Wang, Gunuk; Cho, Byungjin; Kim, Dong-Yu; Hwang, Hyunsang; Lee, Takhee

2009-01-14

The resistive switching characteristics of polyfluorene-derivative polymer material in a sub-micron scale via-hole device structure were investigated. The scalable via-hole sub-microstructure was fabricated using an e-beam lithographic technique. The polymer non-volatile memory devices varied in size from 40 x 40 microm(2) to 200 x 200 nm(2). From the scaling of junction size, the memory mechanism can be attributed to the space-charge-limited current with filamentary conduction. Sub-micron scale polymer memory devices showed excellent resistive switching behaviours such as a large ON/OFF ratio (I(ON)/I(OFF) approximately 10(4)), excellent device-to-device switching uniformity, good sweep endurance, and good retention times (more than 10,000 s). The successful operation of sub-micron scale memory devices of our polyfluorene-derivative polymer shows promise to fabricate high-density polymer memory devices.

Shape-memory polymer foam device for treating aneurysms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ortega, Jason M.; Benett, William J.; Small, Ward

A system for treating an aneurysm in a blood vessel or vein, wherein the aneurysm has a dome, an interior, and a neck. The system includes a shape memory polymer foam in the interior of the aneurysm between the dome and the neck. The shape memory polymer foam has pores that include a first multiplicity of pores having a first pore size and a second multiplicity of pores having a second pore size. The second pore size is larger than said first pore size. The first multiplicity of pores are located in the neck of the aneurysm. The second multiplicitymore » of pores are located in the dome of the aneurysm.« less

Experimental study of thermo-mechanical behavior of a thermosetting shape-memory polymer

NASA Astrophysics Data System (ADS)

Liu, Ruoxuan; Li, Yunxin; Liu, Zishun

2018-01-01

The thermo-mechanical behavior of shape-memory polymers (SMPs) serves for the engineering applications of SMPs. Therefore the understanding of thermo-mechanical behavior of SMPs is of great importance. This paper investigates the influence of loading rate and loading level on the thermo-mechanical behavior of a thermosetting shape-memory polymer through experimental study. A series of cyclic tension tests and shape recovery tests at different loading conditions are performed to study the strain level and strain rate effect. The results of tension tests show that the thermosetting shape-memory polymer will behave as rubber material at temperature lower than the glass transition temperature (Tg) and it can obtain a large shape fix ratio at cyclic loading condition. The shape recovery tests exhibit that loading rate and loading level have little effect on the beginning and ending of shape recovery process of the thermosetting shape-memory polymer. Compared with the material which is deformed at temperature higher than Tg, the material deformed at temperature lower than Tg behaves a bigger recovery speed.

TARGETING POLYMER THERAPEUTICS TO BONE

PubMed Central

Low, Stewart; Kopeček, Jindřich

2012-01-01

An aging population in the developing world has led to an increase in musculoskeletal diseases such as osteoporosis and bone metastases. Left untreated many bone diseases cause debilitating pain and in the case of cancer, death. Many potential drugs are effective in treating diseases but result in side effects preventing their efficacy in the clinic. Bone, however, provides an unique environment of inorganic solids, which can be exploited in order to effectively target drugs to diseased tissue. By integration of bone targeting moieties to drug-carrying water-soluble polymers, the payload to diseased area can be increased while side effects decreased. The realization of clinically relevant bone targeted polymer therapeutics depends on (1) understanding bone targeting moiety interactions, (2) development of controlled drug delivery systems, as well as (3) understanding drug interactions. The latter makes it possible to develop bone targeted synergistic drug delivery systems. PMID:22316530

High-Temperature Shape Memory Polymers

NASA Technical Reports Server (NTRS)

Yoonessi, Mitra; Weiss, Robert A.

2012-01-01

physical conformation changes when exposed to an external stimulus, such as a change in temperature. Such materials have a permanent shape, but can be reshaped above a critical temperature and fixed into a temporary shape when cooled under stress to below the critical temperature. When reheated above the critical temperature (Tc, also sometimes called the triggering or switching temperature), the materials revert to the permanent shape. The current innovation involves a chemically treated (sulfonated, carboxylated, phosphonated, or other polar function group), high-temperature, semicrystalline thermoplastic poly(ether ether ketone) (Tg .140 C, Tm = 340 C) mix containing organometallic complexes (Zn++, Li+, or other metal, ammonium, or phosphonium salts), or high-temperature ionic liquids (e.g. hexafluorosilicate salt with 1-propyl-3- methyl imidazolium, Tm = 210 C) to form a network where dipolar or ionic interactions between the polymer and the low-molecular-weight or inorganic compound forms a complex that provides a physical crosslink. Hereafter, these compounds will be referred to as "additives". The polymer is semicrystalline, and the high-melt-point crystals provide a temporary crosslink that acts as a permanent crosslink just so long as the melting temperature is not exceeded. In this example case, the melting point is .340 C, and the shape memory critical temperature is between 150 and 250 C. PEEK is an engineering thermoplastic with a high Young fs modulus, nominally 3.6 GPa. An important aspect of the invention is the control of the PEEK functionalization (in this example, the sulfonation degree), and the thermal properties (i.e. melting point) of the additive, which determines the switching temperature. Because the compound is thermoplastic, it can be formed into the "permanent" shape by conventional plastics processing operations. In addition, the compound may be covalently cross - linked after forming the permanent shape by S-PEEK by applying ionizing

The Holy Grail of Polymer Therapeutics for Cancer Therapy: An Overview on the Pharmacokinetics and Bio Distribution.

PubMed

Dyawanapelly, Sathish; Junnuthula, Vijayabhaskar Reddy; Singh, AkhileshVikram

2015-01-01

In recent years, multifaceted clinical benefits of polymeric therapeutics have been reported. Over the past decades, cancer has been one of the leading causes of mortality in the world. Many clinically approved chemotherapeutics encounter potential challenges against deadly cancer. Moreover, safety and efficacy of anticancer agents have been limited by undesirable pharmacokinetics and biodistribution. To address these limitations, various polymer drug conjugates are being studied and developed to improve the antitumor efficacy. Among other therapeutics, polymer therapeutics are well established platforms that circumvent anticancer therapeutics from enzymatic metabolism via direct conjugation to therapeutic molecules. Interestingly, polymer therapeutics meets an unmet need of small molecules. Further clinical study showed that polymer-drug conjugation can achieve desired pharmacokinetics and biodistribution properties of several anticancer drugs. The present retrospective review mainly enlightens the most recent preclinical and clinical studies include safety, stability, pharmacokinetic behavior and distribution of polymer therapeutics.

Bioactive factor delivery strategies from engineered polymer hydrogels for therapeutic medicine

PubMed Central

Nguyen, Minh Khanh; Alsberg, Eben

2014-01-01

Polymer hydrogels have been widely explored as therapeutic delivery matrices because of their ability to present sustained, localized and controlled release of bioactive factors. Bioactive factor delivery from injectable biopolymer hydrogels provides a versatile approach to treat a wide variety of diseases, to direct cell function and to enhance tissue regeneration. The innovative development and modification of both natural-(e.g., alginate (ALG), chitosan, hyaluronic acid (HA), gelatin, heparin (HEP), etc.) and synthetic-(e.g., polyesters, polyethyleneimine (PEI), etc.) based polymers has resulted in a variety of approaches to design drug delivery hydrogel systems from which loaded therapeutics are released. This review presents the state-of-the-art in a wide range of hydrogels that are formed though self-assembly of polymers and peptides, chemical crosslinking, ionic crosslinking and biomolecule recognition. Hydrogel design for bioactive factor delivery is the focus of the first section. The second section then thoroughly discusses release strategies of payloads from hydrogels for therapeutic medicine, such as physical incorporation, covalent tethering, affinity interactions, on demand release and/or use of hybrid polymer scaffolds, with an emphasis on the last 5 years. PMID:25242831

Porous inorganic-organic shape memory polymers.

PubMed

Zhang, Dawei; Burkes, William L; Schoener, Cody A; Grunlan, Melissa A

2012-06-21

Thermoresponsive shape memory polymers (SMPs) are a type of stimuli-sensitive materials that switch from a temporary shape back to their permanent shape upon exposure to heat. While the majority of SMPs have been fabricated in the solid form, porous SMP foams exhibit distinct properties and are better suited for certain applications, including some in the biomedical field. Like solid SMPs, SMP foams have been restricted to a limited group of organic polymer systems. In this study, we prepared inorganic-organic SMP foams based on the photochemical cure of a macromer comprised of inorganic polydimethylsiloxane (PDMS) segments and organic poly(ε-caprolactone) (PCL) segments, diacrylated PCL(40)-block-PDMS(37)-block-PCL(40). To achieve tunable pore size with high interconnectivity, the SMP foams were prepared via a refined solvent-casting/particulate-leaching (SCPL) method. By varying design parameters such as degree of salt fusion, macromer concentration in the solvent and salt particle size, the SMP foams with excellent shape memory behavior and tunable pore size, pore morphology, and modulus were obtained.

Porous Shape Memory Polymers

PubMed Central

Hearon, Keith; Singhal, Pooja; Horn, John; Small, Ward; Olsovsky, Cory; Maitland, Kristen C.; Wilson, Thomas S.; Maitland, Duncan J.

2013-01-01

Porous shape memory polymers (SMPs) include foams, scaffolds, meshes, and other polymeric substrates that possess porous three-dimensional macrostructures. Porous SMPs exhibit active structural and volumetric transformations and have driven investigations in fields ranging from biomedical engineering to aerospace engineering to the clothing industry. The present review article examines recent developments in porous SMPs, with focus given to structural and chemical classification, methods of characterization, and applications. We conclude that the current body of literature presents porous SMPs as highly interesting smart materials with potential for industrial use. PMID:23646038

Temperature and electrical memory of polymer fibers

NASA Astrophysics Data System (ADS)

Yuan, Jinkai; Zakri, Cécile; Grillard, Fabienne; Neri, Wilfrid; Poulin, Philippe

2014-05-01

We report in this work studies of the shape memory behavior of polymer fibers loaded with carbon nanotubes or graphene flakes. These materials exhibit enhanced shape memory properties with the generation of a giant stress upon shape recovery. In addition, they exhibit a surprising temperature memory with a peak of generated stress at a temperature nearly equal to the temperature of programming. This temperature memory is ascribed to the presence of dynamical heterogeneities and to the intrinsic broadness of the glass transition. We present recent experiments related to observables other than mechanical properties. In particular nanocomposite fibers exhibit variations of electrical conductivity with an accurate memory. Indeed, the rate of conductivity variations during temperature changes reaches a well defined maximum at a temperature equal to the temperature of programming. Such materials are promising for future actuators that couple dimensional changes with sensing electronic functionalities.

Experimental characterization and computational modeling of unimorph shape memory polymer actuators incorporating transverse curvature in the substrate

NASA Astrophysics Data System (ADS)

Cantrell, Jason T.

This document outlines in detail the research performed by applying shape memory polymers in a generic unimorph actuator configuration. A set of experiments designed to investigate the influence of transverse curvature, the relative widths of shape memory polymer and composite substrates, and shape memory polymer thickness on actuator recoverability after multiple thermo-mechanical cycles is presented in detail. A theoretical model of the moment required to maintain shape fixity with minimal shape retention loss was developed and experimentally validated for unimorph composite actuators of varying cross-sectional areas. Theoretical models were also developed and evaluated to determine the relationship between the materials neutral axes and thermal stability during a thermo-mechanical cycle. Research was conducted on the incorporation of shape memory polymers on micro air vehicle wings to maximize shape fixity and shape recoverability while minimizing the volume of shape memory polymer on the wing surface. Applications based research also included experimentally evaluating the feasibility of shape memory polymers on deployable satellite antenna ribs both with and without resistance heaters which could be utilized to assist in antenna deployment.

Thiol-vinyl systems as shape memory polymers and novel two-stage reactive polymer systems

NASA Astrophysics Data System (ADS)

Nair, Devatha P.

2011-12-01

The focus of this research was to formulate, characterize and tailor the reaction methodologies and material properties of thiol-vinyl systems to develop novel polymer platforms for a range of engineering applications. Thiol-ene photopolymers were demonstrated to exhibit several advantageous characteristics for shape memory polymer systems for a range of biomedical applications. The thiol-ene shape memory polymer systems were tough and flexible as compared to the acrylic control systems with glass transition temperatures between 30 and 40 °C; ideal for actuation at body temperature. The thiol-ene polymers also exhibited excellent shape fixity and a rapid and distinct shape memory actuation response along with free strain recoveries of greater than 96% and constrained stress recoveries of 100%. Additionally, two-stage reactive thiol-acrylate systems were engineered as a polymer platform technology enabling two independent sets of polymer processing and material properties. There are distinct advantages to designing polymer systems that afford two distinct sets of material properties -- an intermediate polymer that would enable optimum handling and processing of the material (stage 1), while maintaining the ability to tune in different, final properties that enable the optimal functioning of the polymeric material (stage 2). To demonstrate the range of applicability of the two-stage reactive systems, three specific applications were demonstrated; shape memory polymers, lithographic impression materials, and optical materials. The thiol-acrylate reactions exhibit a wide range of application versatility due to the range of available thiol and acrylate monomers as well as reaction mechanisms such as Michael Addition reactions and free radical polymerizations. By designing a series of non-stoichiometeric thiol-acrylate systems, a polymer network is initially formed via a base catalyzed 'click' Michael addition reaction. This self-limiting reaction results in a Stage 1

Localized Hyperthermia for Enhanced Targeted Delivery of Polymer Therapeutics

NASA Astrophysics Data System (ADS)

Frazier, Nicholas

It is estimated that in 2016, more than 848,000 new cases of cancer will be diagnosed in men with more than a quarter being prostate cancer and more than 26,000 deaths attributed to this disease. Prostate cancer poses a limited risk when detected at an early stage and treatment of stages II-III has a 5-year survival rate of almost 100%. However, these early-stage cancers can eventually progress and develop into stage IV, dramatically dropping the 5-year survival rate to 28%. Thus, development of a new therapy is needed to fully eliminate these tumors. Combination of heat and chemotherapy improves therapeutic efficacy while allowing for reduced dosing of drugs and limiting side effects. Localized hyperthermia has been used to enhance the delivery of polymer therapeutics to prostate tumors through increased blood flow, vascular permeability, and incorporation of heat shock targeting. This strategy has been shown to increase the delivery and retention of polymer-drug conjugates leading to enhanced efficacy. Although much work has been done using this strategy, the effects of different thermal dosing on polymer accumulation are unknown. The first aim of this research is to examine how altering heating parameters influences polymer tumor accumulation. The hypothesis for this aim is that there is an optimal thermal treatment that leads to the maximal amount of polymer accumulation in the tumors. Additionally, the previously used heating method of plasmonic photothermal therapy (PPTT) can result in long-term accumulation of gold nanoparticles in healthy organs, potentially limiting clinical applicability. The second aim of this proposal will be focused on investigating the alternative method of high intensity focused ultrasound (HIFU) for selective heating of tumors and enhancing macromolecular delivery. HIFU has shown the capability for precise, noninvasive heating of specific regions within the prostate through magnetic resonance imaging (MRI) guidance. The hypothesis

Electric Field Activated Shape Memory Polymer Composite

NASA Technical Reports Server (NTRS)

Kang, Jin Ho (Inventor); Turner, Travis L. (Inventor); Siochi, Emilie J. (Inventor); Penner, Ronald K. (Inventor)

2017-01-01

Provided is an electrically activated shape memory polymer composite capable of thermal shape reformation using electric power to heat the composite through its matrix glass transition temperature. The composite includes an adaptable polymer matrix component using a diglycidyl ether resin, at least one substantially well-dispersed conductive or magnetic nano-filler component, and at least one elastic, laminated layer. Also provided are methods of preparing the composite and methods of activating the composite. A shape reformation of the composite is triggered by applying an electric field at DC and/or at a frequency above about 1.mu.Hz for a sufficient time.

Characterizing Effects of Nitric Oxide Sterilization on tert-Butyl Acrylate Shape Memory Polymers

NASA Astrophysics Data System (ADS)

Phillippi, Ben

As research into the potential uses of shape memory polymers (SMPs) as implantable medical devices continues to grow and expand, so does the need for an accurate and reliable sterilization mechanism. The ability of an SMP to precisely undergo a programmed shape change will define its ability to accomplish a therapeutic task. To ensure proper execution of the in vivo shape change, the sterilization process must not negatively affect the shape memory behavior of the material. To address this need, this thesis investigates the effectiveness of a benchtop nitric oxide (NOx) sterilization process and the extent to which the process affects the shape memory behavior of a well-studied tert-Butyl Acrylate (tBA) SMP. Quantifying the effects on shape memory behavior was performed using a two-tiered analysis. A two-tiered study design was used to determine if the sterilization process induced any premature shape recovery and to identify any effects that NOx has on the overall shape memory behavior of the foams. Determining the effectiveness of the NOx system--specially, whether the treated samples are more sterile/less contaminated than untreated--was also performed with a two-tiered analysis. In this case, the two-tiered analysis was employed to have a secondary check for contamination. To elaborate, all of the samples that were deemed not contaminated from the initial test were put through a second sterility test to check for contamination a second time. The results of these tests indicated the NOx system is an effective sterilization mechanism and the current protocol does not negatively impact the shape memory behavior of the tBA SMP. The samples held their compressed shape throughout the entirety of the sterilization process. Additionally, there were no observable impacts on the shape memory behavior induced by NOx. Lastly, the treated samples demonstrated lower contamination than the untreated. This thesis demonstrates the effectiveness of NOx as a laboratory scale

Therapeutic polymers for dental adhesives: Loading resins with bio-active components

PubMed Central

Imazato, Satoshi; Ma, Sai; Chen, Ji-hua; Xu, Hockin H.K.

2014-01-01

Objectives Many recent adhesives on the market exhibit reasonable clinical performance. Future innovations in adhesive materials should therefore seek out novel properties rather than simply modifying existing technologies. It is proposed that adhesive materials that are “bio-active” could contribute to better prognosis of restorative treatments. Methods This review examines the recent approaches used to achieve therapeutic polymers for dental adhesives by incorporating bio-active components. A strategy to maintain adhesive restorations is the focus of this paper. Results Major trials on therapeutic dental adhesives have looked at adding antibacterial activities or remineralization effects. Applications of antibacterial resin monomers based on quaternary ammonium compounds have received much research attention, and the loading of nano-sized bioactive particles or multiple ion-releasing glass fillers have been perceived as advantageous since they are not expected to influence the mechanical properties of the carrier polymer. Significance The therapeutic polymer approaches described here have the potential to provide clinical benefits. However, not many technological applications in this category have been successfully commercialized. Clinical evidence as well as further advancement of these technologies can be a driving force to make these new types of materials clinically available. PMID:23899387

Drug-releasing shape-memory polymers - the role of morphology, processing effects, and matrix degradation.

PubMed

Wischke, Christian; Behl, Marc; Lendlein, Andreas

2013-09-01

Shape-memory polymers (SMPs) have gained interest for temporary drug-release systems that should be anchored in the body by self-sufficient active movements of the polymeric matrix. Based on the so far published scientific literature, this review highlights three aspects that require particular attention when combining SMPs with drug molecules: i) the defined polymer morphology as required for the shape-memory function, ii) the strong effects that processing conditions such as drug-loading methodologies can have on the drug-release pattern from SMPs, and iii) the independent control of drug release and degradation by their timely separation. The combination of SMPs with a drug-release functionality leads to multifunctional carriers that are an interesting technology for pharmaceutical sciences and can be further expanded by new materials such as thermoplastic SMPs or temperature-memory polymers. Experimental studies should include relevant molecules as (model) drugs and provide a thermomechanical characterization also in an aqueous environment, report on the potential effect of drug type and loading levels on the shape-memory functionality, and explore the potential correlation of polymer degradation and drug release.

Recent advances in degradable lactide-based shape-memory polymers.

PubMed

Balk, Maria; Behl, Marc; Wischke, Christian; Zotzmann, Jörg; Lendlein, Andreas

2016-12-15

Biodegradable polymers are versatile polymeric materials that have a high potential in biomedical applications avoiding subsequent surgeries to remove, for example, an implanted device. In the past decade, significant advances have been achieved with poly(lactide acid) (PLA)-based materials, as they can be equipped with an additional functionality, that is, a shape-memory effect (SME). Shape-memory polymers (SMPs) can switch their shape in a predefined manner upon application of a specific external stimulus. Accordingly, SMPs have a high potential for applications ranging from electronic engineering, textiles, aerospace, and energy to biomedical and drug delivery fields based on the perspectives of new capabilities arising with such materials in biomedicine. This study summarizes the progress in SMPs with a particular focus on PLA, illustrates the design of suitable homo- and copolymer structures as well as the link between the (co)polymer structure and switching functionality, and describes recent advantages in the implementation of novel switching phenomena into SMP technology. Copyright © 2016 Elsevier B.V. All rights reserved.

Capacitance-voltage measurement in memory devices using ferroelectric polymer

NASA Astrophysics Data System (ADS)

Nguyen, Chien A.; Lee, Pooi See

2006-01-01

Application of thin polymer film as storing mean for non-volatile memory devices is investigated. Capacitance-voltage (C-V) measurement of metal-ferroelectric-metal device using ferroelectric copolymer P(VDF-TrFE) as dielectric layer shows stable 'butter-fly' curve. The two peaks in C-V measurement corresponding to the largest capacitance are coincidental at the coercive voltages that give rise to zero polarization in the polarization hysteresis measurement. By comparing data of C-V and P-E measurement, a correlation between two types of hysteresis is established in which it reveals simultaneous electrical processes occurring inside the device. These processes are caused by the response of irreversible and reversible polarization to the applied electric field that can be used to present a memory window. The memory effect of ferroelectric copolymer is further demonstrated for fabricating polymeric non-volatile memory devices using metal-ferroelectric-insulator-semiconductor structure (MFIS). By applying different sweeping voltages at the gate, bidirectional flat-band voltage shift is observed in the ferroelectric capacitor. The asymmetrical shift after negative sweeping is resulted from charge accumulation at the surface of Si substrate caused by the dipole direction in the polymer layer. The effect is reversed for positive voltage sweeping.

Nanoscale porosity in polymer films: fabrication and therapeutic applications

PubMed Central

Bernards, Daniel A.; Desai, Tejal A.

2011-01-01

This review focuses on current developments in the field of nanostructured bulk polymers and their application in bioengineering and therapeutic sciences. In contrast to well-established nanoscale materials, such as nanoparticles and nanofibers, bulk nanostructured polymers combine nanoscale structure in a macroscopic construct, which enables unique application of these materials. Contemporary fabrication and processing techniques capable of producing nanoporous polymer films are reviewed. Focus is placed on techniques capable of sub-100 nm features since this range approaches the size scale of biological components, such as proteins and viruses. The attributes of these techniques are compared, with an emphasis on the characteristic advantages and limitations of each method. Finally, application of these materials to biofiltration, immunoisolation, and drug delivery are reviewed. PMID:22140398

High performance shape memory polymer networks based on rigid nanoparticle cores

PubMed Central

Song, Jie

2010-01-01

Smart materials that can respond to external stimuli are of widespread interest in biomedical science. Thermal-responsive shape memory polymers, a class of intelligent materials that can be fixed at a temporary shape below their transition temperature (Ttrans) and thermally triggered to resume their original shapes on demand, hold great potential as minimally invasive self-fitting tissue scaffolds or implants. The intrinsic mechanism for shape memory behavior of polymers is the freezing and activation of the long-range motion of polymer chain segments below and above Ttrans, respectively. Both Ttrans and the extent of polymer chain participation in effective elastic deformation and recovery are determined by the network composition and structure, which are also defining factors for their mechanical properties, degradability, and bioactivities. Such complexity has made it extremely challenging to achieve the ideal combination of a Ttrans slightly above physiological temperature, rapid and complete recovery, and suitable mechanical and biological properties for clinical applications. Here we report a shape memory polymer network constructed from a polyhedral oligomeric silsesquioxane nanoparticle core functionalized with eight polyester arms. The cross-linked networks comprising this macromer possessed a gigapascal-storage modulus at body temperature and a Ttrans between 42 and 48 °C. The materials could stably hold their temporary shapes for > 1 year at room temperature and achieve full shape recovery ≤ 51 °C in a matter of seconds. Their versatile structures allowed for tunable biodegradability and biofunctionalizability. These materials have tremendous promise for tissue engineering applications. PMID:20375285

Reconfigurable and Reprocessable Thermoset Shape Memory Polymer with Synergetic Triple Dynamic Covalent Bonds.

PubMed

Wang, Yongwei; Pan, Yi; Zheng, Zhaohui; Ding, Xiaobin

2018-04-20

Degradable shape memory polymers (SMPs), especially for polyurethane-based SMPs, have shown great potential for biomedical applications. How to reasonably fabricate SMPs with the ideal combination of degradability, shape reconfigurability, and reprocessability is a critical issue and remains a challenge for medical disposable materials. Herein, a shape memory poly(urethane-urea) with synergetic triple dynamic covalent bonds is reported via embedding polycaprolactone unit into poly(urethane-urea) with the hindered urea dynamic bond. The single polymer network is biodegradable, thermadapt, and reprocessable, without sacrificing the outstanding shape memory performance. Such a shape memory network with plasticity and reprocessability is expected to have significant and positive impact on the medical device industry. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape memory polymer sensors for tracking cumulative environmental exposure

NASA Astrophysics Data System (ADS)

Snyder, Ryan; Rauscher, Michael; Vining, Ben; Havens, Ernie; Havens, Teresa; McFerran, Jace

2010-04-01

Cornerstone Research Group Inc. (CRG) has developed environmental exposure tracking (EET) sensors using shape memory polymers (SMP) to monitor the degradation of perishable items, such as munitions, foods and beverages, or medicines, by measuring the cumulative exposure to temperature and moisture. SMPs are polymers whose qualities have been altered to give them dynamic shape "memory" properties. Under thermal or moisture stimuli, the SMP exhibits a radical change from a rigid thermoset to a highly flexible, elastomeric state. The dynamic response of the SMP can be tailored to match the degradation profile of the perishable item. SMP-based EET sensors require no digital memory or internal power supply and provide the capability of inexpensive, long-term life cycle monitoring of thermal and moisture exposure over time. This technology was developed through Phase I and Phase II SBIR efforts with the Navy. The emphasis of current research centers on transitioning SMP materials from the lab bench to a production environment. Here, CRG presents the commercialization progress of thermally-activated EET sensors, focusing on fabrication scale-up, process refinements, and quality control. In addition, progress on the development of vapor pressure-responsive SMP (VPR-SMP) will be discussed.

Triple-Shape Memory Polymers Based on Self-Complementary Hydrogen Bonding

PubMed Central

Ware, Taylor; Hearon, Keith; Lonnecker, Alexander; Wooley, Karen L.; Maitland, Duncan J.; Voit, Walter

2012-01-01

Triple shape memory polymers (TSMPs) are a growing subset of a class of smart materials known as shape memory polymers, which are capable of changing shape and stiffness in response to a stimulus. A TSMP can change shapes twice and can fix two metastable shapes in addition to its permanent shape. In this work, a novel TSMP system comprised of both permanent covalent cross-links and supramolecular hydrogen bonding cross-links has been synthesized via a one-pot method. Triple shape properties arise from the combination of the glass transition of (meth)acrylate copolymers and the dissociation of self-complementary hydrogen bonding moieties, enabling broad and independent control of both glass transition temperature (Tg) and cross-link density. Specifically, ureidopyrimidone methacrylate and a novel monomer, ureidopyrimidone acrylate, were copolymerized with various alkyl acrylates and bisphenol A ethoxylate diacrylate. Control of Tg from 0 to 60 °C is demonstrated: concentration of hydrogen bonding moieties is varied from 0 to 40 wt %; concentration of the diacrylate is varied from 0 to 30 wt %. Toughness ranges from 0.06 to 0.14 MPa and is found to peak near 20 wt % of the supramolecular cross-linker. A widely tunable class of amorphous triple-shape memory polymers has been developed and characterized through dynamic and quasi-static thermomechanical testing to gain insights into the dynamics of supramolecular networks. PMID:22287811

Characterization of origami shape memory metamaterials (SMMM) made of bio-polymer blends

NASA Astrophysics Data System (ADS)

Kshad, Mohamed Ali E.; Naguib, Hani E.

2016-04-01

Shape memory materials (SMMs) are materials that can return to their virgin state and release mechanically induced strains by external stimuli. Shape memory polymers (SMPs) are a class of SMMs that show a high shape recoverability and which have attractive potential for structural applications. In this paper, we experimentally study the shape memory effect of origami based metamaterials. The main focus is on the Muira origami metamaterials. The fabrication technique used to produce origami structure is direct molding where all the geometrical features are molded from thermally virgin polymers without post folding of flat sheets. The study shows experimental investigations of shape memory metamaterials (SMMMs) made of SMPs that can be used in different applications such as medicine, robotics, and lightweight structures. The origami structure made from SMP blends, activated with uniform heating. The effect of blend composition on the shape memory behavior was studied. Also the influence of the thermomechanical and the viscoelastic properties of origami unit cell on the activation process have been discussed, and stress relaxation and shape recovery were investigated. Activation process of the unit cell has been demonstrated.

Optical Input/Electrical Output Memory Elements based on a Liquid Crystalline Azobenzene Polymer.

PubMed

Mosciatti, Thomas; Bonacchi, Sara; Gobbi, Marco; Ferlauto, Laura; Liscio, Fabiola; Giorgini, Loris; Orgiu, Emanuele; Samorì, Paolo

2016-03-01

Responsive polymer materials can change their properties when subjected to external stimuli. In this work, thin films of thermotropic poly(metha)acrylate/azobenzene polymers are explored as active layer in light-programmable, electrically readable memories. The memory effect is based on the reversible modifications of the film morphology induced by the photoisomerization of azobenzene mesogenic groups. When the film is in the liquid crystalline phase, the trans → cis isomerization induces a major surface reorganization on the mesoscopic scale that is characterized by a reduction in the effective thickness of the film. The film conductivity is measured in vertical two-terminal devices in which the polymer is sandwiched between a Au contact and a liquid compliant E-GaIn drop. We demonstrate that the trans → cis isomerization is accompanied by a reversible 100-fold change in the film conductance. In this way, the device can be set in a high- or low-resistance state by light irradiation at different wavelengths. This result paves the way toward the potential use of poly(metha)acrylate/azobenzene polymer films as active layer for optical input/electrical output memory elements.

Biomedical Applications of Thermally Activated Shape Memory Polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small IV, W; Singhal, P; Wilson, T S

2009-04-10

Shape memory polymers (SMPs) are smart materials that can remember a primary shape and can return to this primary shape from a deformed secondary shape when given an appropriate stimulus. This property allows them to be delivered in a compact form via minimally invasive surgeries in humans, and deployed to achieve complex final shapes. Here we review the various biomedical applications of SMPs and the challenges they face with respect to actuation and biocompatibility. While shape memory behavior has been demonstrated with heat, light and chemical environment, here we focus our discussion on thermally stimulated SMPs.

3D Printing of Shape Memory Polymers for Flexible Electronic Devices.

PubMed

Zarek, Matt; Layani, Michael; Cooperstein, Ido; Sachyani, Ela; Cohn, Daniel; Magdassi, Shlomo

2016-06-01

The formation of 3D objects composed of shape memory polymers for flexible electronics is described. Layer-by-layer photopolymerization of methacrylated semicrystalline molten macromonomers by a 3D digital light processing printer enables rapid fabrication of complex objects and imparts shape memory functionality for electrical circuits. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shape-memory effect by specific biodegradable polymer blending for biomedical applications.

PubMed

Cha, Kook Jin; Lih, Eugene; Choi, Jiyeon; Joung, Yoon Ki; Ahn, Dong Jun; Han, Dong Keun

2014-05-01

Specific biodegradable polymers having shape-memory properties through "polymer-blend" method are investigated and their shape-switching in body temperature (37 °C) is characterized. Poly(L-lactide-co-caprolactone) (PLCL) and poly(L-lactide-co-glycolide) (PLGA) are dissolved in chloroform and the films of several blending ratios of PLCL/PLGA are prepared by solvent casting. The shape-memory properties of films are also examined using dynamic mechanical analysis (DMA). Among the blending ratios, the PLCL50/PLGA50 film shows good performance of shape-fixity and shape-recovery based on glass transition temperature. It displays that the degree of shape recovery is 100% at 37 °C and the shape recovery proceeds within only 15 s. In vitro biocompatibility studies are shown to have good blood compatibility and cytocompatibility for the PLCL50/PLGA50 films. It is expected that this blended biodegradable polymer can be potentially used as a material for blood-contacting medical devices such as a self-expended vascular polymer stents and vascular closure devices in biomedical applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lipid-polymer hybrid nanoparticle-mediated therapeutics delivery: advances and challenges.

PubMed

Bose, Rajendran J C; Ravikumar, Rramaswamy; Karuppagounder, Vengadeshprabu; Bennet, Devasier; Rangasamy, Sabarinathan; Thandavarayan, Rajarajan A

2017-08-01

With rapid advances in nanomedicine, lipid-polymer hybrid nanoparticles (LPHNPs) have emerged as promising nanocarriers for several biomedical applications, including therapeutics delivery and biomedical imaging. Significant research has been dedicated to biomimetic or targeting functionalization, as well as controlled and image-guided drug-release capabilities. Despite this research, the clinical translation of LPHNP-mediated therapeutics delivery has progressed incrementally. In this review, we discuss the recent advances in and challenges to the development and application of LPHNPs, present examples to demonstrate the advantages of LPHNPs in therapeutics delivery and imaging applications, and discuss the translational obstacles to LPHNP technology. Copyright © 2017. Published by Elsevier Ltd.

Improving the in vivo therapeutic index of siRNA polymer conjugates through increasing pH responsiveness.

PubMed

Guidry, Erin N; Farand, Julie; Soheili, Arash; Parish, Craig A; Kevin, Nancy J; Pipik, Brenda; Calati, Kathleen B; Ikemoto, Nori; Waldman, Jacob H; Latham, Andrew H; Howell, Bonnie J; Leone, Anthony; Garbaccio, Robert M; Barrett, Stephanie E; Parmar, Rubina Giare; Truong, Quang T; Mao, Bing; Davies, Ian W; Colletti, Steven L; Sepp-Lorenzino, Laura

2014-02-19

Polymer based carriers that aid in endosomal escape have proven to be efficacious siRNA delivery agents in vitro and in vivo; however, most suffer from cytotoxicity due in part to a lack of selectivity for endosomal versus cell membrane lysis. For polymer based carriers to move beyond the laboratory and into the clinic, it is critical to find carriers that are not only efficacious, but also have margins that are clinically relevant. In this paper we report three distinct categories of polymer conjugates that improve the selectivity of endosomal membrane lysis by relying on the change in pH associated with endosomal trafficking, including incorporation of low pKa heterocycles, acid cleavable amino side chains, or carboxylic acid pH sensitive charge switches. Additionally, we determine the therapeutic index of our polymer conjugates in vivo and demonstrate that the incorporation of pH responsive elements dramatically expands the therapeutic index to 10-15, beyond that of the therapeutic index (less than 3), for polymer conjugates previously reported.

Towards Low-Cost Effective and Homogeneous Thermal Activation of Shape Memory Polymers

PubMed Central

Lantada, Andrés Díaz; Rebollo, María Ángeles Santamaría

2013-01-01

A typical limitation of intelligent devices based on the use of shape-memory polymers as actuators is linked to the widespread use of distributed heating resistors, via Joule effect, as activation method, which involves several relevant issues needing attention, such as: (a) Final device size is importantly increased due to the additional space required for the resistances; (b) the use of resistances limits materials’ strength and the obtained devices are normally weaker; (c) the activation process through heating resistances is not homogeneous, thus leading to important temperature differences among the polymeric structure and to undesirable thermal gradients and stresses, also limiting the application fields of shape-memory polymers. In our present work we describe interesting activation alternatives, based on coating shape-memory polymers with different kinds of conductive materials, including textiles, conductive threads and conductive paint, which stand out for their easy, rapid and very cheap implementation. Distributed heating and homogeneous activation can be achieved in several of the alternatives studied and the technical results are comparable to those obtained by using advanced shape-memory nanocomposites, which have to deal with complex synthesis, processing and security aspects. Different combinations of shape memory epoxy resin with several coating electrotextiles, conductive films and paints are prepared, simulated with the help of thermal finite element method based resources and characterized using infrared thermography for validating the simulations and overall design process. A final application linked to an active catheter pincer is detailed and the advantages of using distributed heating instead of conventional resistors are discussed. PMID:28788401

Strategic design and fabrication of acrylic shape memory polymers

NASA Astrophysics Data System (ADS)

Park, Ju Hyuk; Kim, Hansu; Ryoun Youn, Jae; Song, Young Seok

2017-08-01

Modulation of thermomechanics nature is a critical issue for an optimized use of shape memory polymers (SMPs). In this study, a strategic approach was proposed to control the transition temperature of SMPs. Free radical vinyl polymerization was employed for tailoring and preparing acrylic SMPs. Transition temperatures of the shape memory tri-copolymers were tuned by changing the composition of monomers. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy analyses were carried out to evaluate the chemical structures and compositions of the synthesized SMPs. The thermomechanical properties and shape memory performance of the SMPs were also examined by performing dynamic mechanical thermal analysis. Numerical simulation based on a finite element method provided consistent results with experimental cyclic shape memory tests of the specimens. Transient shape recovery tests were conducted and optical transparence of the samples was identified. We envision that the materials proposed in this study can help develop a new type of shape-memory devices in biomedical and aerospace engineering applications.

Air-stable memory array of bistable rectifying diodes based on ferroelectric-semiconductor polymer blends

NASA Astrophysics Data System (ADS)

Kumar, Manasvi; Sharifi Dehsari, Hamed; Anwar, Saleem; Asadi, Kamal

2018-03-01

Organic bistable diodes based on phase-separated blends of ferroelectric and semiconducting polymers have emerged as promising candidates for non-volatile information storage for low-cost solution processable electronics. One of the bottlenecks impeding upscaling is stability and reliable operation of the array in air. Here, we present a memory array fabricated with an air-stable amine-based semiconducting polymer. Memory diode fabrication and full electrical characterizations were carried out in atmospheric conditions (23 °C and 45% relative humidity). The memory diodes showed on/off ratios greater than 100 and further exhibited robust and stable performance upon continuous write-read-erase-read cycles. Moreover, we demonstrate a 4-bit memory array that is free from cross-talk with a shelf-life of several months. Demonstration of the stability and reliable air operation further strengthens the feasibility of the resistance switching in ferroelectric memory diodes for low-cost applications.

Molecular engineering of proteins and polymers for targeting and intracellular delivery of therapeutics.

PubMed

Stayton, P S; Hoffman, A S; Murthy, N; Lackey, C; Cheung, C; Tan, P; Klumb, L A; Chilkoti, A; Wilbur, F S; Press, O W

2000-03-01

There are many protein and DNA based therapeutics under development in the biotechnology and pharmaceutical industries. Key delivery challenges remain before many of these biomolecular therapeutics reach the clinic. Two important barriers are the effective targeting of drugs to specific tissues and cells and the subsequent intracellular delivery to appropriate cellular compartments. In this review, we summarize protein engineering work aimed at improving the stability and refolding efficiency of antibody fragments used in targeting, and at constructing new streptavidin variants which may offer improved performance in pre-targeting delivery strategies. In addition, we review recent work with pH-responsive polymers that mimic the membrane disruptive properties of viruses and toxins. These polymers could serve as alternatives to fusogenic peptides in gene therapy formulations and to enhance the intracellular delivery of protein therapeutics that function in the cytoplasm.

Polymer therapeutics at a crossroads? Finding the path for improved translation in the twenty-first century.

PubMed

Duncan, Ruth

Despite the relatively small early investment, first generation 'polymer therapeutics' have been remarkably successful with more than 25 products licenced for human use as polymeric drugs, sequestrants, conjugates, and as an imaging agent. Many exhibit both clinical and commercial success with new concepts already in clinical trials. Nevertheless after four decades of evolution, this field is arriving at an important crossroads. Over the last decade, the landscape has changed rapidly. There are an increasing number of failed clinical trials, the number of 'copy' and 'generic' products is growing (danger of ignoring the biological rationale for design and suppression of innovation), potential drawbacks of PEG are becoming more evident, and the 'nanomedicine' boom has brought danger of loss of scientific focus/hype. Grasping opportunities provided by advances in understanding of the patho-physiology and molecular basis of diseases, new polymer/conjugate synthetic and analytical methods, as well as the large database of clinical experience will surely ensure a successful future for innovative polymer therapeutics. Progress will, however, be in jeopardy if polymer safety is overlooked in respect of the specific route of administration/clinical use, poorly characterised materials/formulations are used to define biological or early clinical properties, and if clinical trial protocols fail to select patients most likely to benefit from these macromolecular therapeutics. Opportunities to improve clinical trial design for polymer-anticancer drug conjugates are discussed. This short personal perspective summarises some of the important challenges facing polymer therapeutics in R&D today, and future opportunities to improve successful translation.

Design and Verification of a Shape Memory Polymer Peripheral Occlusion Device

PubMed Central

Landsman, Todd L.; Bush, Ruth L.; Glowczwski, Alan; Horn, John; Jessen, Staci L.; Ungchusri, Ethan; Diguette, Katelin; Smith, Harrison R.; Hasan, Sayyeda M.; Nash, Daniel; Clubb, Fred J.; Maitland, Duncan J.

2017-01-01

Shape memory polymer foams have been previously investigated for their safety and efficacy in treating a porcine aneurysm model. Their biocompatibility, rapid thrombus formation, and ability for endovascular catheter-based delivery to a variety of vascular beds makes these foams ideal candidates for use in numerous embolic applications, particularly within the peripheral vasculature. This study sought to investigate the material properties, safety, and efficacy of a shape memory polymer peripheral embolization device in vitro. The material characteristics of the device were analyzed to show tunability of the glass transition temperature (Tg) and the expansion rate of the polymer to ensure adequate time to deliver the device through a catheter prior to excessive foam expansion. Mechanical analysis and flow migration studies were performed to ensure minimal risk of vessel perforation and undesired thromboembolism upon device deployment. The efficacy of the device was verified by performing blood flow studies that established affinity for thrombus formation and blood penetration throughout the foam and by delivery of the device in an ultrasound phantom that demonstrated flow stagnation and diversion of flow to collateral pathways. PMID:27419615

Shape memory polymer network with thermally distinct elasticity and plasticity.

PubMed

Zhao, Qian; Zou, Weike; Luo, Yingwu; Xie, Tao

2016-01-01

Stimuli-responsive materials with sophisticated yet controllable shape-changing behaviors are highly desirable for real-world device applications. Among various shape-changing materials, the elastic nature of shape memory polymers allows fixation of temporary shapes that can recover on demand, whereas polymers with exchangeable bonds can undergo permanent shape change via plasticity. We integrate the elasticity and plasticity into a single polymer network. Rational molecular design allows these two opposite behaviors to be realized at different temperature ranges without any overlap. By exploring the cumulative nature of the plasticity, we demonstrate easy manipulation of highly complex shapes that is otherwise extremely challenging. The dynamic shape-changing behavior paves a new way for fabricating geometrically complex multifunctional devices.

Shape memory polymer network with thermally distinct elasticity and plasticity

PubMed Central

Zhao, Qian; Zou, Weike; Luo, Yingwu; Xie, Tao

2016-01-01

Stimuli-responsive materials with sophisticated yet controllable shape-changing behaviors are highly desirable for real-world device applications. Among various shape-changing materials, the elastic nature of shape memory polymers allows fixation of temporary shapes that can recover on demand, whereas polymers with exchangeable bonds can undergo permanent shape change via plasticity. We integrate the elasticity and plasticity into a single polymer network. Rational molecular design allows these two opposite behaviors to be realized at different temperature ranges without any overlap. By exploring the cumulative nature of the plasticity, we demonstrate easy manipulation of highly complex shapes that is otherwise extremely challenging. The dynamic shape-changing behavior paves a new way for fabricating geometrically complex multifunctional devices. PMID:26824077

Therapeutic affect reduction, emotion regulation, and emotional memory reconsolidation: A neuroscientific quandary.

PubMed

LaBar, Kevin S

2015-01-01

Lane et al. emphasize the role of emotional arousal as a precipitating factor for successful psychotherapy. However, as therapy ensues, the arousal diminishes. How can the unfolding therapeutic process generate long-term memories for reconsolidated emotional material without the benefit of arousal? Studies investigating memory for emotionally regulated material provide some clues regarding the neural pathways that may underlie therapy-based memory reconsolidation.

Thermally responsive polymer systems for self-healing, reversible adhesion and shape memory applications

NASA Astrophysics Data System (ADS)

Luo, Xiaofan

Responsive polymers are "smart" materials that are capable of performing prescribed, dynamic functions under an applied stimulus. In this dissertation, we explore several novel design strategies to develop thermally responsive polymers and polymer composites for self-healing, reversible adhesion and shape memory applications. In the first case described in Chapters 2 and 3, a thermally triggered self-healing material was prepared by blending a high-temperature epoxy resin with a thermoplastic polymer, poly(epsilon-caprolactone) (PCL). The initially miscible system undergoes polymerization induced phase separation (PIPS) during the curing of epoxy and yields a variety of compositionally dependent morphologies. At a particular PCL loading, the cured blend displays a "bricks-and-mortar" morphology in which epoxy exists as interconnected spheres ("bricks") within a continuous PCL matrix ("mortar"). A heat induced "bleeding" phenomenon was observed in the form of spontaneous wetting of all free surfaces by the molten PCL, and is attributed to the volumetric thermal expansion of PCL above its melting point in excess of epoxy brick expansion, which we term differential expansive bleeding (DEB). This DEB is capable of healing damage such as cracks. In controlled self-healing experiments, heating of a cracked specimen led to PCL bleeding from the bulk that yields a liquid layer bridging the crack gap. Upon cooling, a "scar" composed of PCL crystals was formed at the site of the crack, restoring a significant portion of mechanical strength. We further utilized DEB to enable strong and thermally-reversible adhesion of the material to itself and to metallic substrates, without any requirement for macroscopic softening or flow. After that, Chapters 4--6 present a novel composite strategy for the design and fabrication of shape memory polymer composites. The basic approach involves physically combining two or more functional components into an interpenetrating fiber

Photonic Shape Memory Polymer with Stable Multiple Colors

PubMed Central

2017-01-01

A photonic shape memory polymer film that shows large color response (∼155 nm) in a wide temperature range has been fabricated from a semi-interpenetrating network of a cholesteric polymer and poly(benzyl acrylate). The large color response is achieved by mechanical embossing of the photonic film above its broad glass transition temperature. The embossed film, as it recovers to its original shape on heating through the broad thermal transition, exhibits multiple structural colors ranging from blue to orange. The relaxation behavior of the embossed film can be fully described using a Kelvin–Voigt model, which reveals that the influence of temperature on the generation of colors is much stronger than that of time, thereby producing stable multiple colors. PMID:28840717

Ultra-low power, highly uniform polymer memory by inserted multilayer graphene electrode

NASA Astrophysics Data System (ADS)

Jang, Byung Chul; Seong, Hyejeong; Kim, Jong Yun; Koo, Beom Jun; Kim, Sung Kyu; Yang, Sang Yoon; Gap Im, Sung; Choi, Sung-Yool

2015-12-01

Filament type resistive random access memory (RRAM) based on polymer thin films is a promising device for next generation, flexible nonvolatile memory. However, the resistive switching nonuniformity and the high power consumption found in the general filament type RRAM devices present critical issues for practical memory applications. Here, we introduce a novel approach not only to reduce the power consumption but also to improve the resistive switching uniformity in RRAM devices based on poly(1,3,5-trimethyl-3,4,5-trivinyl cyclotrisiloxane) by inserting multilayer graphene (MLG) at the electrode/polymer interface. The resistive switching uniformity was thereby significantly improved, and the power consumption was markedly reduced by 250 times. Furthermore, the inserted MLG film enabled a transition of the resistive switching operation from unipolar resistive switching to bipolar resistive switching and induced self-compliance behavior. The findings of this study can pave the way toward a new area of application for graphene in electronic devices.

Polymer Therapeutics: Biomarkers and New Approaches for Personalized Cancer Treatment.

PubMed

Atkinson, Stuart P; Andreu, Zoraida; Vicent, María J

2018-01-23

Polymer therapeutics (PTs) provides a potentially exciting approach for the treatment of many diseases by enhancing aqueous solubility and altering drug pharmacokinetics at both the whole organism and subcellular level leading to improved therapeutic outcomes. However, the failure of many polymer-drug conjugates in clinical trials suggests that we may need to stratify patients in order to match each patient to the right PT. In this concise review, we hope to assess potential PT-specific biomarkers for cancer treatment, with a focus on new studies, detection methods, new models and the opportunities this knowledge will bring for the development of novel PT-based anti-cancer strategies. We discuss the various "hurdles" that a given PT faces on its passage from the syringe to the tumor (and beyond), including the passage through the bloodstream, tumor targeting, tumor uptake and the intracellular release of the active agent. However, we also discuss other relevant concepts and new considerations in the field, which we hope will provide new insight into the possible applications of PT-related biomarkers.

Polymer Therapeutics: Biomarkers and New Approaches for Personalized Cancer Treatment

PubMed Central

Atkinson, Stuart P.; Andreu, Zoraida; Vicent, María J.

2018-01-01

Polymer therapeutics (PTs) provides a potentially exciting approach for the treatment of many diseases by enhancing aqueous solubility and altering drug pharmacokinetics at both the whole organism and subcellular level leading to improved therapeutic outcomes. However, the failure of many polymer-drug conjugates in clinical trials suggests that we may need to stratify patients in order to match each patient to the right PT. In this concise review, we hope to assess potential PT-specific biomarkers for cancer treatment, with a focus on new studies, detection methods, new models and the opportunities this knowledge will bring for the development of novel PT-based anti-cancer strategies. We discuss the various “hurdles” that a given PT faces on its passage from the syringe to the tumor (and beyond), including the passage through the bloodstream, tumor targeting, tumor uptake and the intracellular release of the active agent. However, we also discuss other relevant concepts and new considerations in the field, which we hope will provide new insight into the possible applications of PT-related biomarkers. PMID:29360800

Tunable thiol-epoxy shape memory polymer foams

NASA Astrophysics Data System (ADS)

Ellson, Gregory; Di Prima, Matthew; Ware, Taylor; Tang, Xiling; Voit, Walter

2015-05-01

Shape memory polymers (SMPs) are uniquely suited to a number of applications due to their shape storage and recovery abilities and the wide range of available chemistries. However, many of the desired performance properties are tied to the polymer chemistry which can make optimization difficult. The use of foaming techniques is one way to tune mechanical response of an SMP without changing the polymer chemistry. In this work, a novel thiol-epoxy SMP was foamed using glass microspheres (40 and 50% by volume Q-Cel 6019), using expandable polymer microspheres (1% 930 DU 120), and by a chemical blowing agent (1% XOP-341). Each approach created SMP foam with a differing density and microstructure from the others. Thermal and thermomechanical analysis was performed to observe the behavioral difference between the foaming techniques and to confirm that the glass transition (Tg) was relatively unchanged near 50 °C while the glassy modulus varied from 19.1 to 345 MPa and the rubbery modulus varied from 0.04 to 2.2 MPa. The compressive behavior of the foams was characterized through static compression testing at different temperatures, and cyclic compression testing at Tg. Constrained shape recovery testing showed a range of peak recovery stress from 5 MPa for the syntactic Q-Cel foams to ˜0.1 MPa for the chemically blown XOP-341 foam. These results showed that multiple foaming approaches can be used with a novel SMP to vary the mechanical response independent of Tg and polymer chemistry.

Polymer therapeutics and the EPR effect.

PubMed

Maeda, Hiroshi

History of the EPR (enhanced permeability and retention) effect is discussed, which goes back to the analyses of molecular pathology in bacterial infection and edema (extravasation) formation. The first mediator we found for extravasation was bradykinin. Later on, were found nitric oxide and superoxide, then formation of peroxynitrite, that activates procollagenase. In this inflammatory setting many other vascular mediators are involved that are also common to cancer vasculature. Obviously cancer vasculature is defective architechtally, and this makes macromolecular drugs more permeable through the vascular wall. The importance of this pathophysiological event of EPR effect can be applied to macromolecular drug-delivery, or tumor selective delivery, which takes hours to achieve in the primary as well as metastatic tumors, not to mention of the inflamed tissues. The retention of the EPR means that such drugs will be retained in tumor tissues more than days to weeks. This was demonstrated initially, and most dramatically, using SMANCS, a protein-polymer conjugated-drug dissolved in lipid contrast medium (Lipiodol) by administering intraarterially. For disseminating the EPR concept globally, or in the scientific community, Professor Ruth Duncan played a key role at the early stage, as she worked extensively on polymer- therapeutics, and knew its importance.

Estimation of aneurysm wall stresses created by treatment with a shape memory polymer foam device

PubMed Central

Hwang, Wonjun; Volk, Brent L.; Akberali, Farida; Singhal, Pooja; Criscione, John C.

2012-01-01

In this study, compliant latex thin-walled aneurysm models are fabricated to investigate the effects of expansion of shape memory polymer foam. A simplified cylindrical model is selected for the in-vitro aneurysm, which is a simplification of a real, saccular aneurysm. The studies are performed by crimping shape memory polymer foams, originally 6 and 8 mm in diameter, and monitoring the resulting deformation when deployed into 4-mm-diameter thin-walled latex tubes. The deformations of the latex tubes are used as inputs to physical, analytical, and computational models to estimate the circumferential stresses. Using the results of the stress analysis in the latex aneurysm model, a computational model of the human aneurysm is developed by changing the geometry and material properties. The model is then used to predict the stresses that would develop in a human aneurysm. The experimental, simulation, and analytical results suggest that shape memory polymer foams have potential of being a safe treatment for intracranial saccular aneurysms. In particular, this work suggests oversized shape memory foams may be used to better fill the entire aneurysm cavity while generating stresses below the aneurysm wall breaking stresses. PMID:21901546

Design and verification of a shape memory polymer peripheral occlusion device.

PubMed

Landsman, Todd L; Bush, Ruth L; Glowczwski, Alan; Horn, John; Jessen, Staci L; Ungchusri, Ethan; Diguette, Katelin; Smith, Harrison R; Hasan, Sayyeda M; Nash, Daniel; Clubb, Fred J; Maitland, Duncan J

2016-10-01

Shape memory polymer foams have been previously investigated for their safety and efficacy in treating a porcine aneurysm model. Their biocompatibility, rapid thrombus formation, and ability for endovascular catheter-based delivery to a variety of vascular beds makes these foams ideal candidates for use in numerous embolic applications, particularly within the peripheral vasculature. This study sought to investigate the material properties, safety, and efficacy of a shape memory polymer peripheral embolization device in vitro. The material characteristics of the device were analyzed to show tunability of the glass transition temperature (Tg) and the expansion rate of the polymer to ensure adequate time to deliver the device through a catheter prior to excessive foam expansion. Mechanical analysis and flow migration studies were performed to ensure minimal risk of vessel perforation and undesired thromboembolism upon device deployment. The efficacy of the device was verified by performing blood flow studies that established affinity for thrombus formation and blood penetration throughout the foam and by delivery of the device in an ultrasound phantom that demonstrated flow stagnation and diversion of flow to collateral pathways. Copyright © 2016 Elsevier Ltd. All rights reserved.

An investigation of a thermally steerable electroactive polymer/shape memory polymer hybrid actuator

NASA Astrophysics Data System (ADS)

Ren, Kailiang; Bortolin, Robert S.; Zhang, Q. M.

2016-02-01

This paper investigates the thermal response of a hybrid actuator composed of an electroactive polymer (EAP) and a shape memory polymer (SMP). This study introduces the concept of using the large strain from a phase transition (ferroelectric to paraelectric phase) induced by temperature change in a poly(vinylidene fluoride-trifluoroethylene) film to tune the shape of an SMP film above its glass transition temperature (Tg). Based on the material characterization data, it is revealed that the thickness ratio of the EAP/SMP films plays a critical role in the displacement of the actuator. Further, it is also demonstrated that the displacement of the hybrid actuator can be tailored by varying the temperature, and finite element method simulation results fit well with the measurement data. This specially designed hybrid actuator shows great promise for future morphing aircraft applications.

Characterization of Nonlinear Rate Dependent Response of Shape Memory Polymers

NASA Technical Reports Server (NTRS)

Volk, Brent; Lagoudas, Dimitris C.; Chen, Yi-Chao; Whitley, Karen S.

2007-01-01

Shape Memory Polymers (SMPs) are a class of polymers, which can undergo deformation in a flexible state at elevated temperatures, and when cooled below the glass transition temperature, while retaining their deformed shape, will enter and remain in a rigid state. Upon heating above the glass transition temperature, the shape memory polymer will return to its original, unaltered shape. SMPs have been reported to recover strains of over 400%. It is important to understand the stress and strain recovery behavior of SMPs to better develop constitutive models which predict material behavior. Initial modeling efforts did not account for large deformations beyond 25% strain. However, a model under current development is capable of describing large deformations of the material. This model considers the coexisting active (rubber) and frozen (glass) phases of the polymer, as well as the transitions between the material phases. The constitutive equations at the continuum level are established with internal state variables to describe the microstructural changes associated with the phase transitions. For small deformations, the model reduces to a linear model that agrees with those reported in the literature. Thermomechanical characterization is necessary for the development, calibration, and validation of a constitutive model. The experimental data reported in this paper will assist in model development by providing a better understanding of the stress and strain recovery behavior of the material. This paper presents the testing techniques used to characterize the thermomechanical material properties of a shape memory polymer (SMP) and also presents the resulting data. An innovative visual-photographic apparatus, known as a Vision Image Correlation (VIC) system was used to measure the strain. The details of this technique will also be presented in this paper. A series of tensile tests were performed on specimens such that strain levels of 10, 25, 50, and 100% were applied to

Mechanical analysis of carbon fiber reinforced shape memory polymer composite for self-deployable structure in space environment

NASA Astrophysics Data System (ADS)

Hong, Seok Bin; Ahn, Yong San; Jang, Joon Hyeok; Kim, Jin-Gyun; Goo, Nam Seo; Yu, Woong-Ryeol

2016-04-01

Shape memory polymer (SMP) is one of smart polymers which exhibit shape memory effect upon external stimuli. Reinforcements as carbon fiber had been used for making shape memory polymer composite (CF-SMPC). This study investigated a possibility of designing self-deployable structures in harsh space condition using CF-SMPCs and analyzed their shape memory behaviors with constitutive equation model.CF-SMPCs were prepared using woven carbon fabrics and a thermoset epoxy based SMP to obtain their basic mechanical properties including actuation in harsh environment. The mechanical and shape memory properties of SMP and CF-SMPCs were characterized using dynamic mechanical analysis (DMA) and universal tensile machine (UTM) with an environmental chamber. The mechanical properties such as flexural strength and tensile strength of SMP and CF-SMPC were measured with simple tensile/bending test and time dependent shape memory behavior was characterized with designed shape memory bending test. For mechanical analysis of CF-SMPCs, a 3D constitutive equation of SMP, which had been developed using multiplicative decomposition of the deformation gradient and shape memory strains, was used with material parameters determined from CF-SMPCs. Carbon fibers in composites reinforced tensile and flexural strength of SMP and acted as strong elastic springs in rheology based equation models. The actuation behavior of SMP matrix and CF-SMPCs was then simulated as 3D shape memory bending cases. Fiber bundle property was imbued with shell model for more precise analysis and it would be used for prediction of deploying behavior in self-deployable hinge structure.

Shape Memory Polymers for Body Motion Energy Harvesting and Self-Powered Mechanosensing.

PubMed

Liu, Ruiyuan; Kuang, Xiao; Deng, Jianan; Wang, Yi-Cheng; Wang, Aurelia C; Ding, Wenbo; Lai, Ying-Chih; Chen, Jun; Wang, Peihong; Lin, Zhiqun; Qi, H Jerry; Sun, Baoquan; Wang, Zhong Lin

2018-02-01

Growing demand in portable electronics raises a requirement to electronic devices being stretchable, deformable, and durable, for which functional polymers are ideal choices of materials. Here, the first transformable smart energy harvester and self-powered mechanosensation sensor using shape memory polymers is demonstrated. The device is based on the mechanism of a flexible triboelectric nanogenerator using the thermally triggered shape transformation of organic materials for effectively harvesting mechanical energy. This work paves a new direction for functional polymers, especially in the field of mechanosensation for potential applications in areas such as soft robotics, biomedical devices, and wearable electronics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bulk heterojunction polymer memory devices with reduced graphene oxide as electrodes.

PubMed

Liu, Juqing; Yin, Zongyou; Cao, Xiehong; Zhao, Fei; Lin, Anping; Xie, Linghai; Fan, Quli; Boey, Freddy; Zhang, Hua; Huang, Wei

2010-07-27

A unique device structure with a configuration of reduced graphene oxide (rGO) /P3HT:PCBM/Al has been designed for the polymer nonvolatile memory device. The current-voltage (I-V) characteristics of the fabricated device showed the electrical bistability with a write-once-read-many-times (WORM) memory effect. The memory device exhibits a high ON/OFF ratio (10(4)-10(5)) and low switching threshold voltage (0.5-1.2 V), which are dependent on the sheet resistance of rGO electrode. Our experimental results confirm that the carrier transport mechanisms in the OFF and ON states are dominated by the thermionic emission current and ohmic current, respectively. The polarization of PCBM domains and the localized internal electrical field formed among the adjacent domains are proposed to explain the electrical transition of the memory device.

Sugar-based amphiphilic polymers for biomedical applications: from nanocarriers to therapeutics.

PubMed

Gu, Li; Faig, Allison; Abdelhamid, Dalia; Uhrich, Kathryn

2014-10-21

Various therapeutics exhibit unfavorable physicochemical properties or stability issues that reduce their in vivo efficacy. Therefore, carriers able to overcome such challenges and deliver therapeutics to specific in vivo target sites are critically needed. For instance, anticancer drugs are hydrophobic and require carriers to solubilize them in aqueous environments, and gene-based therapies (e.g., siRNA or pDNA) require carriers to protect the anionic genes from enzymatic degradation during systemic circulation. Polymeric micelles, which are self-assemblies of amphiphilic polymers (APs), constitute one delivery vehicle class that has been investigated for many biomedical applications. Having a hydrophobic core and a hydrophilic shell, polymeric micelles have been used as drug carriers. While traditional APs are typically comprised of nondegradable block copolymers, sugar-based amphiphilic polymers (SBAPs) synthesized by us are comprised of branched, sugar-based hydrophobic segments and a hydrophilic poly(ethylene glycol) chain. Similar to many amphiphilic polymers, SBAPs self-assemble into polymeric micelles. These nanoscale micelles have extremely low critical micelle concentrations offering stability against dilution, which occurs with systemic administration. In this Account, we illustrate applications of SBAPs for anticancer drug delivery via physical encapsulation within SBAP micelles and chemical conjugation to form SBAP prodrugs capable of micellization. Additionally, we show that SBAPs are excellent at stabilizing liposomal delivery systems. These SBAP-lipid complexes were developed to deliver hydrophobic anticancer therapeutics, achieving preferential uptake in cancer cells over normal cells. Furthermore, these complexes can be designed to electrostatically complex with gene therapies capable of transfection. Aside from serving as a nanocarrier, SBAPs have also demonstrated unique bioactivity in managing atherosclerosis, a major cause of cardiovascular

Thermally driven microfluidic pumping via reversible shape memory polymers

NASA Astrophysics Data System (ADS)

Robertson, J. M.; Rodriguez, R. X.; Holmes, L. R., Jr.; Mather, P. T.; Wetzel, E. D.

2016-08-01

The need exists for autonomous microfluidic pumping systems that utilize environmental cues to transport fluid within a network of channels for such purposes as heat distribution, self-healing, or optical reconfiguration. Here, we report on reversible thermally driven microfluidic pumping enabled by two-way shape memory polymers. After developing a suitable shape memory polymer (SMP) through variation in the crosslink density, thin and flexible microfluidic devices were constructed by lamination of plastic films with channels defined by laser-cutting of double-sided adhesive film. SMP blisters integrated into the devices provide thermally driven pumping, while opposing elastic blisters are used to generate backpressure for reversible operation. Thermal cycling of the device was found to drive reversible fluid flow: upon heating to 60 °C, the SMP rapidly contracted to fill the surface channels with a transparent fluid, and upon cooling to 8 °C the flow reversed and the channel re-filled with black ink. Combined with a metallized backing layer, this device results in refection of incident light at high temperatures and absorption of light (at the portions covered with channels) at low temperatures. We discuss power-free, autonomous applications ranging from thermal regulation of structures to thermal indication via color change.

Multimaterial 4D Printing with Tailorable Shape Memory Polymers

PubMed Central

Ge, Qi; Sakhaei, Amir Hosein; Lee, Howon; Dunn, Conner K.; Fang, Nicholas X.; Dunn, Martin L.

2016-01-01

We present a new 4D printing approach that can create high resolution (up to a few microns), multimaterial shape memory polymer (SMP) architectures. The approach is based on high resolution projection microstereolithography (PμSL) and uses a family of photo-curable methacrylate based copolymer networks. We designed the constituents and compositions to exhibit desired thermomechanical behavior (including rubbery modulus, glass transition temperature and failure strain which is more than 300% and larger than any existing printable materials) to enable controlled shape memory behavior. We used a high resolution, high contrast digital micro display to ensure high resolution of photo-curing methacrylate based SMPs that requires higher exposure energy than more common acrylate based polymers. An automated material exchange process enables the manufacture of 3D composite architectures from multiple photo-curable SMPs. In order to understand the behavior of the 3D composite microarchitectures, we carry out high fidelity computational simulations of their complex nonlinear, time-dependent behavior and study important design considerations including local deformation, shape fixity and free recovery rate. Simulations are in good agreement with experiments for a series of single and multimaterial components and can be used to facilitate the design of SMP 3D structures. PMID:27499417

Preventive and therapeutic effect of treadmill running on chronic stress-induced memory deficit in rats.

PubMed

Radahmadi, Maryam; Alaei, Hojjatallah; Sharifi, Mohammad Reza; Hosseini, Nasrin

2015-04-01

Previous results indicated that stress impairs learning and memory. In this research, the effects of preventive, therapeutic and regular continually running activity on chronic stress-induced memory deficit in rats were investigated. 70 male rats were randomly divided into seven groups as follows: Control, Sham, Stress-Rest, Rest-Stress, Stress-Exercise, Exercise-Stress and Exercise-Stress & Exercise groups. Chronic restraint stress was applied 6 h/day for 21days and treadmill running 1 h/day. Memory function was evaluated by the passive avoidance test. The results revealed that running activities had therapeutic effect on mid and long-term memory deficit and preventive effects on short and mid-term memory deficit in stressed rats. Regular continually running activity improved mid and long-term memory compared to Exercise-Stress group. The beneficial effects of exercise were time-dependent in stress conditions. Finally, data corresponded to the possibility that treadmill running had a more important role on treatment rather than on prevention on memory impairment induced by stress. Copyright © 2014 Elsevier Ltd. All rights reserved.

Demonstrating the importance of polymer-conjugate conformation in solution on its therapeutic output: Diethylstilbestrol (DES)-polyacetals as prostate cancer treatment.

PubMed

Giménez, Vanessa; James, Craig; Armiñán, Ana; Schweins, Ralf; Paul, Alison; Vicent, María J

2012-04-30

The design of improved polymeric carriers to be used in the next generation of polymer therapeutics is an ongoing challenge. Biodegradable systems present potential advantages regarding safety benefit apart from the possibility to use higher molecular weight (Mw) carriers allowing PK optimization, by exploiting the enhanced permeability and retention (EPR)-mediated tumor targeting. Within this context, we previously designed pH-responsive polyacetalic systems, tert-polymers, where a drug with the adequate diol-functionality was incorporated within the polymer mainchain. The synthetic, non-steroidal estrogen, diethylstilboestrol (DES) clinically used for the treatment of advanced prostate cancer was chosen as drug. In order to improve the properties of this tert-polymer, novel polyacetalic systems as block-co-polymers, with more defined structure have been obtained. This second generation polyacetals allowed higher drug capacity than the tert-polymer, a biphasic DES release profile at acidic pH and due to its controlled amphiphilic character readily formed micelle-like structures in solution. These features result in an enhancement of conjugate therapeutic value in selected prostate cancer cell models. Exhaustive physico-chemical characterization focusing on nanoconjugate solution behavior and using advanced techniques, such as, pulsed-gradient spin-echo NMR (PGSE-NMR) and small-angle neutron scattering (SANS), has been carried out in order to demonstrate this hypothesis. Clear evidence of significantly different conformation in solution has been obtained for both polyacetals. These results demonstrate that an adequate control on molecular or supramolecular conformation in solution with polymer therapeutics is crucial in order to achieve the desired therapeutic output. Copyright © 2012 Elsevier B.V. All rights reserved.

Epitaxial Growth of Thin Ferroelectric Polymer Films on Graphene Layer for Fully Transparent and Flexible Nonvolatile Memory.

PubMed

Kim, Kang Lib; Lee, Wonho; Hwang, Sun Kak; Joo, Se Hun; Cho, Suk Man; Song, Giyoung; Cho, Sung Hwan; Jeong, Beomjin; Hwang, Ihn; Ahn, Jong-Hyun; Yu, Young-Jun; Shin, Tae Joo; Kwak, Sang Kyu; Kang, Seok Ju; Park, Cheolmin

2016-01-13

Enhancing the device performance of organic memory devices while providing high optical transparency and mechanical flexibility requires an optimized combination of functional materials and smart device architecture design. However, it remains a great challenge to realize fully functional transparent and mechanically durable nonvolatile memory because of the limitations of conventional rigid, opaque metal electrodes. Here, we demonstrate ferroelectric nonvolatile memory devices that use graphene electrodes as the epitaxial growth substrate for crystalline poly(vinylidene fluoride-trifluoroethylene) (PVDF-TrFE) polymer. The strong crystallographic interaction between PVDF-TrFE and graphene results in the orientation of the crystals with distinct symmetry, which is favorable for polarization switching upon the electric field. The epitaxial growth of PVDF-TrFE on a graphene layer thus provides excellent ferroelectric performance with high remnant polarization in metal/ferroelectric polymer/metal devices. Furthermore, a fully transparent and flexible array of ferroelectric field effect transistors was successfully realized by adopting transparent poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] semiconducting polymer.

Nonvolatile memory characteristics of organic thin film transistors using poly(2-hydroxyethyl methacrylate)-based polymer multilayer dielectric

NASA Astrophysics Data System (ADS)

Chen, Ying-Chih; Su, Yan-Kuin; Yu, Hsin-Chieh; Huang, Chun-Yuan; Huang, Tsung-Syun

2011-10-01

A wide hysteresis width characteristic (memory window) was observed in the organic thin film transistors (OTFTs) using poly(2-hydroxyethyl methacrylate) (PHEMA)-based polymer multilayers. In this study, a strong memory effect was also found in the pentacene-based OTFTs and the electric characteristics were improved by introducing PHEMA/poly(methyl methacrylate) (PMMA)/PHEMA trilayer to replace the conventional PHEMA monolayer or PMMA/PHEMA and PHEMA/PMMA bilayer as the dielectric layers of OTFTs. The memory effect was originated from the electron trapping and slow polarization of the dielectrics. The hydroxyl (-OH) groups inside the polymer dielectric were the main charge storage sites of the electrons. This charge-storage phenomenon could lead to a wide flat-band voltage shift (memory window, △VFB = 22 V) which is essential for the OTFTs' memory-related applications. Moreover, the fabricated transistors also exhibited significant switchable channel current due to the charge-storage and slow charge relaxation.

Interventional Application of Shape Memory Polymer Foam Final Report CRADA No. TC-02067-03

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maitland, D.; Metzger, M. F.

This was a collaborative effort between The Regents of the University of California, Lawrence Livermore National Laboratory (LLNL) and Sierra Interventions, LLC, to develop shape memory polymer foam devices for treating hemorrhagic stroke.

New design strategy for reversible plasticity shape memory polymers with deformable glassy aggregates.

PubMed

Lin, Tengfei; Tang, Zhenghai; Guo, Baochun

2014-12-10

Reversible plasticity shape memory (RPSM) is a new concept in the study of shape memory performance behavior and describes a phenomenon in which shape memory polymers (SMPs) can undergo a large plastic deformation at room temperature and subsequently recover their original shape upon heating. To date, RPSM behavior has been demonstrated in only a few polymers. In the present study, we implement a new design strategy, in which deformable glassy hindered phenol (AO-80) aggregates are incorporated into an amorphous network of epoxidized natural rubber (ENR) cured with zinc diacrylate (ZDA), in order to achieve RPSM properties. We propose that AO-80 continuously tunes the glass transition temperature (Tg) and improves the chain mobility of the SMP, providing traction and anchoring the ENR chains by intermolecular hydrogen bonding interactions. The RPSM behavior of the amorphous SMPs is characterized, and the results demonstrate good fixity at large deformations (up to 300%) and excellent recovery upon heating. Large energy storage capacities at Td in these RPSM materials are demonstrated compared with those achieved at elevated temperature in traditional SMPs. Interestingly, the further revealed self-healing properties of these materials are closely related to their RPSM behavior.

Thermoreversible Folding as a Route to the Unique Shape-Memory Character in Ductile Polymer Networks.

PubMed

McBride, Matthew K; Podgorski, Maciej; Chatani, Shunsuke; Worrell, Brady T; Bowman, Christopher N

2018-06-21

Ductile, cross-linked films were folded as a means to program temporary shapes without the need for complex heating cycles or specialized equipment. Certain cross-linked polymer networks, formed here with the thiol-isocyanate reaction, possessed the ability to be pseudoplastically deformed below the glass transition, and the original shape was recovered during heating through the glass transition. To circumvent the large forces required to plastically deform a glassy polymer network, we have utilized folding, which localizes the deformation in small creases, and achieved large dimensional changes with simple programming procedures. In addition to dimension changes, three-dimensional objects such as swans and airplanes were developed to demonstrate applying origami principles to shape memory. We explored the fundamental mechanical properties that are required to fold polymer sheets and observed that a yield point that does not correspond to catastrophic failure is required. Unfolding occurred during heating through the glass transition, indicating the vitrification of the network that maintained the temporary, folded shape. Folding was demonstrated as a powerful tool to simply and effectively program ductile shape-memory polymers without the need for thermal cycling.

On the Takayanagi principle for the shape memory effect and thermomechanical behaviors in polymers with multi-phases

NASA Astrophysics Data System (ADS)

Lu, Haibao; Yu, Kai; Huang, Wei Min; Leng, Jinsong

2016-12-01

We present an explicit model to study the mechanics and physics of the shape memory effect (SME) in polymers based on the Takayanagi principle. The molecular structural characteristics and elastic behavior of shape memory polymers (SMPs) with multi-phases are investigated in terms of the thermomechanical properties of the individual components, of which the contributions are combined by using Takayanagi’s series-parallel model and parallel-series model, respectively. After that, Boltzmann superposition principle is employed to couple the multi-SME, elastic modulus parameter (E) and temperature parameter (T) in SMPs. Furthermore, the extended Takayanagi model is proposed to separate the plasticizing effect and physical swelling effect on the thermo-/chemo-responsive SME in polymers and then compared with the available experimental data reported in the literature. This study is expected to provide a powerful simulation tool for modeling and experimental substantiation of the mechanics and working mechanism of SME in polymers.

The future orientation of constructive memory: an evolutionary perspective on therapeutic hypnosis and brief psychotherapy.

PubMed

Rossi, Ernest; Erickson-Klein, Roxanna; Rossi, Kathryn

2008-04-01

We explore a new distinction between the future, prospective memory system being investigated in current neuroscience and the past, retrospective memory system, which was the original theoretical foundation of therapeutic hypnosis, classical psychoanalysis, and psychotherapy. We then generalize a current evolutionary theory of sleep and dreaming, which focuses on the future, prospective memory system, to conceptualize a new evolutionary perspective on therapeutic hypnosis and brief psychotherapy. The implication of current neuroscience research is that activity-dependent gene expression and brain plasticity are the psychobiological basis of adaptive behavior, consciousness, and creativity in everyday life as well as psychotherapy. We summarize a case illustrating how this evolutionary perspective can be used to quickly resolve problems with past obstructive procrastination in school to facilitate current and future academic success.

Envisioning the future of polymer therapeutics for brain disorders.

PubMed

Rodriguez-Otormin, Fernanda; Duro-Castano, Aroa; Conejos-Sánchez, Inmaculada; Vicent, María J

2018-06-14

The growing incidence of brain-related pathologies and the problems that undermine the development of efficient and effective treatments have prompted both researchers and the pharmaceutical industry to search for novel therapeutic alternatives. Polymer therapeutics (PT) display properties well suited to the treatment of neuro-related disorders, which help to overcome the many hidden obstacles on the journey to the central nervous system (CNS). The inherent features of PT, derived from drug(s) conjugation, in parallel with the progress in synthesis and analytical methods, the increasing knowledge in molecular basis of diseases, and collected clinical data through the last four decades, have driven the translation from "bench to bedside" for various biomedical applications. However, since the approval of Gliadel® wafers, little progress has been made in the CNS field, even though brain targeting represents an ever-growing challenge. A thorough assessment of the steps required for successful brain delivery via different administration routes and the consideration of the disease-specific hallmarks are essential to progress in the field. Within this review, we hope to summarize the latest developments, successes, and failures and discuss considerations on designs and strategies for PT in the treatment of CNS disorders. This article is categorized under: Therapeutic Approaches and Drug Discovery > Nanomedicine for Neurological Disease Nanotechnology Approaches to Biology > Nanoscale Systems in Biology Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease. © 2018 Wiley Periodicals, Inc.

Deformation behavior of carbon-fiber reinforced shape-memory-polymer composites used for deployable structures (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lan, Xin; Liu, Liwu; Li, Fengfeng; Pan, Chengtong; Liu, Yanju; Leng, Jinsong

2017-04-01

Shape memory polymers (SMPs) are a new type of smart material, they perform large reversible deformation with a certain external stimulus (e.g., heat and electricity). The properties (e.g., stiffness, strength and other mechanically static or quasi-static load-bearing capacity) are primarily considered for conventional resin-based composite materials which are mainly used for structural materials. By contrast, the mechanical actuating performance with finite deformation is considered for the shape memory polymers and their composites which can be used for both structural materials and functional materials. For shape memory polymers and their composites, the performance of active deformation is expected to further promote the development in smart active deformation structures, such as deployable space structures and morphing wing aircraft. The shape memory polymer composites (SMPCs) are also one type of High Strain Composite (HSC). The space deployable structures based on carbon fiber reinforced shape memory polymer composites (SMPCs) show great prospects. Considering the problems that SMPCs are difficult to meet the practical applications in space deployable structures in the recent ten years, this paper aims to research the mechanics of deformation, actuation and failure of SMPCs. In the overall view of the shape memory polymer material's nonlinearity (nonlinearity and stress softening in the process of pre-deformation and recovery, relaxation in storage process, irreversible deformation), by the multiple verifications among theory, finite element and experiments, one obtains the deformation and actuation mechanism for the process of "pre-deformation, energy storage and actuation" and its non-fracture constraint domain. Then, the parameters of SMPCs will be optimized. Theoretical analysis is realized by the strain energy function, additionally considering the interaction strain energy between the fiber and the matrix. For the common resin-based or soft

Electroactive polymer and shape memory alloy actuators in biomimetics and humanoids

NASA Astrophysics Data System (ADS)

Tadesse, Yonas

2013-04-01

There is a strong need to replicate natural muscles with artificial materials as the structure and function of natural muscle is optimum for articulation. Particularly, the cylindrical shape of natural muscle fiber and its interconnected structure promote the critical investigation of artificial muscles geometry and implementation in the design phase of certain platforms. Biomimetic robots and Humanoid Robot heads with Facial Expressions (HRwFE) are some of the typical platforms that can be used to study the geometrical effects of artificial muscles. It has been shown that electroactive polymer and shape memory alloy artificial muscles and their composites are some of the candidate materials that may replicate natural muscles and showed great promise for biomimetics and humanoid robots. The application of these materials to these systems reveals the challenges and associated technologies that need to be developed in parallel. This paper will focus on the computer aided design (CAD) models of conductive polymer and shape memory alloys in various biomimetic systems and Humanoid Robot with Facial Expressions (HRwFE). The design of these systems will be presented in a comparative manner primarily focusing on three critical parameters: the stress, the strain and the geometry of the artificial muscle.

Frequency-controlled wireless shape memory polymer microactuator for drug delivery application.

PubMed

Zainal, M A; Ahmad, A; Mohamed Ali, M S

2017-03-01

This paper reports the wireless Shape-Memory-Polymer actuator operated by external radio frequency magnetic fields and its application in a drug delivery device. The actuator is driven by a frequency-sensitive wireless resonant heater which is bonded directly to the Shape-Memory-Polymer and is activated only when the field frequency is tuned to the resonant frequency of heater. The heater is fabricated using a double-sided Cu-clad Polyimide with much simpler fabrication steps compared to previously reported methods. The actuation range of 140 μm as the tip opening distance is achieved at device temperature 44 °C in 30 s using 0.05 W RF power. A repeatability test shows that the actuator's average maximum displacement is 110 μm and standard deviation of 12 μm. An experiment is conducted to demonstrate drug release with 5 μL of an acidic solution loaded in the reservoir and the device is immersed in DI water. The actuator is successfully operated in water through wireless activation. The acidic solution is released and diffused in water with an average release rate of 0.172 μL/min.

Therapeutic limitations in tumor-specific CD8+ memory T cell engraftment

PubMed Central

Bathe, Oliver F; Dalyot-Herman, Nava; Malek, Thomas R

2003-01-01

Background Adoptive immunotherapy with cytotoxic T lymphocytes (CTL) represents an alternative approach to treating solid tumors. Ideally, this would confer long-term protection against tumor. We previously demonstrated that in vitro-generated tumor-specific CTL from the ovalbumin (OVA)-specific OT-I T cell receptor transgenic mouse persisted long after adoptive transfer as memory T cells. When recipient mice were challenged with the OVA-expressing E.G7 thymoma, tumor growth was delayed and sometimes prevented. The reasons for therapeutic failures were not clear. Methods OT-I CTL were adoptively transferred to C57BL/6 mice 21 – 28 days prior to tumor challenge. At this time, the donor cells had the phenotypical and functional characteristics of memory CD8+ T cells. Recipients which developed tumor despite adoptive immunotherapy were analyzed to evaluate the reason(s) for therapeutic failure. Results Dose-response studies demonstrated that the degree of tumor protection was directly proportional to the number of OT-I CTL adoptively transferred. At a low dose of OT-I CTL, therapeutic failure was attributed to insufficient numbers of OT-I T cells that persisted in vivo, rather than mechanisms that actively suppressed or anergized the OT-I T cells. In recipients of high numbers of OT-I CTL, the E.G7 tumor that developed was shown to be resistant to fresh OT-I CTL when examined ex vivo. Furthermore, these same tumor cells no longer secreted a detectable level of OVA. In this case, resistance to immunotherapy was secondary to selection of clones of E.G7 that expressed a lower level of tumor antigen. Conclusions Memory engraftment with tumor-specific CTL provides long-term protection against tumor. However, there are several limitations to this immunotherapeutic strategy, especially when targeting a single antigen. This study illustrates the importance of administering large numbers of effectors to engraft sufficiently efficacious immunologic memory. It also

Direct Writing of Three-Dimensional Macroporous Photonic Crystals on Pressure-Responsive Shape Memory Polymers.

PubMed

Fang, Yin; Ni, Yongliang; Leo, Sin-Yen; Wang, Bingchen; Basile, Vito; Taylor, Curtis; Jiang, Peng

2015-10-28

Here we report a single-step direct writing technology for making three-dimensional (3D) macroporous photonic crystal patterns on a new type of pressure-responsive shape memory polymer (SMP). This approach integrates two disparate fields that do not typically intersect: the well-established templating nanofabrication and shape memory materials. Periodic arrays of polymer macropores templated from self-assembled colloidal crystals are squeezed into disordered arrays in an unusual shape memory "cold" programming process. The recovery of the original macroporous photonic crystal lattices can be triggered by direct writing at ambient conditions using both macroscopic and nanoscopic tools, like a pencil or a nanoindenter. Interestingly, this shape memory disorder-order transition is reversible and the photonic crystal patterns can be erased and regenerated hundreds of times, promising the making of reconfigurable/rewritable nanooptical devices. Quantitative insights into the shape memory recovery of collapsed macropores induced by the lateral shear stresses in direct writing are gained through fundamental investigations on important process parameters, including the tip material, the critical pressure and writing speed for triggering the recovery of the deformed macropores, and the minimal feature size that can be directly written on the SMP membranes. Besides straightforward applications in photonic crystal devices, these smart mechanochromic SMPs that are sensitive to various mechanical stresses could render important technological applications ranging from chromogenic stress and impact sensors to rewritable high-density optical data storage media.

A New Strategy to Prepare Polymer-based Shape Memory Elastomers.

PubMed

Song, Shijie; Feng, Jiachun; Wu, Peiyi

2011-10-04

A new strategy that utilizes the microphase separation of block copolymer and phase transition of small molecules for preparing polymer-based shape memory elastomer has been proposed. According to this strategy, a novel kind of shape memory elastomer comprising styrene-b-(ethylene-co-butylene)-b-styrene (SEBS) and paraffin has been prepared. Because paraffins are midblock-selective molecules for SEBS, they will preferentially enter and swell EB blocks supporting paraffins as an excellent switch phase for shape memory effect. Microstructures of SEBS/paraffin composites have been characterized by transmission electron microscopy, polarized light microscopy, and differential scanning calorimetry. The composites demonstrate various phase morphologies with regard to different paraffin loading. It has been found that under low paraffin loading, all the paraffins precisely embed in and swell EB-rich domains. While under higher loading, part of the paraffins become free and a larger-scaled phase separation has been observed. However, within wide paraffin loadings, all composites show good shape fixing, shape recovery performances, and improved tensile properties. Compared to the reported methods for shape memory elastomers preparation, this method not only simplifies the fabrication procedure from raw materials to processing but also offers a controllable approach for the optimization of shape memory properties as well as balancing the rigidity and softness of the material. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biodegradable shape-memory block co-polymers for fast self-expandable stents.

PubMed

Xue, Liang; Dai, Shiyao; Li, Zhi

2010-11-01

Block co-polymers PCTBVs (M(n) of 36,300-65,300 g/mol, T(m) of 39-40 and 142 degrees C) containing hyperbranched three-arm poly(epsilon-caprolactone) (PCL) as switching segment and microbial polyester PHBV as crystallizable hard segment were designed as biodegradable shape-memory polymer (SMP) for fast self-expandable stent and synthesized in 96% yield by the reaction of three-arm PCL-triol (M(n) of 4200 g/mol, T(m) of 47 degrees C) with methylene diphenyl 4,4'-diisocyanate isocynate (MDI) to form the hyperbrached MDI-linked PCL (PTCM; M(n) of 25,400 g/mol and a T(m) of 38 degrees C), followed by further polymerization with PHBV-diol (M(n) of 2200 g/mol, T(m) of 137 and 148 degrees C). The polymers were characterized by (1)H NMR, GPC, DSC, tensile test, and cyclic thermomechanical tensile test. PCTBVs showed desired thermal properties, mechanical properties, and ductile nature. PCTBV containing 25 wt% PHBV (PCTBV-25) demonstrated excellent shape-memory property at 40 degrees C, with R(f) of 94%, R(r) of 98%, and shape recovery within 25s. PCTBV-25 was also shown as a safe material with good biocompatibility by cytotoxicity tests and cell growth experiments. The stent made from PCTBV-25 film showed nearly complete self-expansion at 37 degrees C within only 25 s, which is much better and faster than the best known self-expandable stents. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Mechanical properties and shape memory effect of thermal-responsive polymer based on PVA

NASA Astrophysics Data System (ADS)

Lin, Liulan; Zhang, Lingfeng; Guo, Yanwei

2018-01-01

In this study, the effect of content of glutaraldehyde (GA) on the shape memory behavior of a shape memory polymer based on polyvinyl alcohol chemically cross-linked with GA was investigated. Thermal-responsive shape memory composites with three different GA levels, GA-PVA (3 wt%, 5 wt%, 7 wt%), were prepared by particle melting, mold forming and freeze-drying technique. The mechanical properties, thermal properties and shape memory behavior were measured by differential scanning calorimeter, physical bending test and cyclic thermo-mechanical test. The addition of GA to PVA led to a steady shape memory transition temperature and an improved mechanical compressive strength. The composite with 5 wt% of GA exhibited the best shape recoverability. Further increase in the crosslinking agent content of GA would reduce the recovery force and prolong the recovery time due to restriction in the movement of the soft PVA chain segments. These results provide important information for the study on materials in 4D printing.

Self-healing nanocomposite using shape memory polymer and carbon nanotubes

NASA Astrophysics Data System (ADS)

Liu, Yingtao; Rajadas, Abhishek; Chattopadhyay, Aditi

2013-04-01

Carbon fiber reinforced composites are used in a wide range of applications in aerospace, mechanical, and civil structures. Due to the nature of material, most damage in composites, such as delaminations, are always barely visible to the naked eye, which makes it difficult to detect and repair. The investigation of biological systems has inspired the development and characterization of self-healing composites. This paper presents the development of a new type of self-healing material in order to impede damage progression and conduct in-situ damage repair in composite structures. Carbon nanotubes, which are highly conductive materials, are mixed with shape memory polymer to develop self-healing capability. The developed polymeric material is applied to carbon fiber reinforced composites to automatically heal the delamination between different layers. The carbon fiber reinforced composite laminates are manufactured using high pressure molding techniques. Tensile loading is applied to double cantilever beam specimens using an MTS hydraulic test frame. A direct current power source is used to generate heat within the damaged area. The application of thermal energy leads to re-crosslinking in shape memory polymers. Experimental results showed that the developed composite materials are capable of healing the matrix cracks and delaminations in the bonded areas of the test specimens. The developed self-healing material has the potential to be used as a novel structural material in mechanical, civil, aerospace applications.

On a novel self-regulating shape memory polymer composite

NASA Astrophysics Data System (ADS)

Gao, Fei; Son, Seyul; Park, Kyungmook; Biggs, David; Andrews, Courtney; Mockensturm, Eric M.; Goulbourne, Nakhiah C.

2011-04-01

Polyurethane shape memory polymers (PU-SMPs) are active materials that can be transformed into complex shapes with the ability to recover their original shape even after undergoing large deformations. Because of their light weight, large recoverability, low cost, and high compliance, SMPs can be potentially employed as actuators, MEMS devices, temperature sensors, and damping elements to name a few. One of the key challenges in implementing SMPs is the response time which is limited by the method of heating and cooling and the material. Unlike shape memory alloys, SMPs can be activated by multiple stimuli including lasers, resistive heating, electric fields, and magnetic fields. While these methods may provide an efficient way of heating the SMP, they rely on the slow process of passive conduction for cooling. In this paper, a self regulating SMP (SR-SMP) composite is introduced, whereby a novel heating and cooling system consisting of embedded silica capillary tubes in the SMP (DiAPLEX® MP4510: SMP Technologies, Inc.) has been developed. The tubes are used to pump hot/cold fluid through the SMP membrane and hence provide a local temperature source. In order to show the effectiveness and efficiency of the mechanism, the thermomechanical response of the SR-SMP is compared experimentally to a SMP with "conventional" i.e. global heating and cooling mechanisms. It is shown that the SR-SMP has a faster thermomechanical response. It has been demonstrated previously that soft SMPs can be controlled by an electric field while in the rubbery phase, thus taking advantage of the Maxwell stress or electrostatic stress effect. Thermomechanical characterization of PU-SMPs is described for different weight percentages of resin (Diphenylmethane-4, 4'-diisocyanate) and hardener (1,4-Butanediol). Varying the percent hardener reduced the effective cross-link density of the polymer and hence the thermomechanical properties. The electromechanical response of pure SMP and SR-SMP is

Field enhanced charge carrier reconfiguration in electronic and ionic coupled dynamic polymer resistive memory.

PubMed

Zhao, Jun Hui; Thomson, Douglas J; Pilapil, Matt; Pillai, Rajesh G; Rahman, G M Aminur; Freund, Michael S

2010-04-02

Dynamic resistive memory devices based on a conjugated polymer composite (PPy(0)DBS(-)Li(+) (PPy: polypyrrole; DBS(-): dodecylbenzenesulfonate)), with field-driven ion migration, have been demonstrated. In this work the dynamics of these systems has been investigated and it has been concluded that increasing the applied field can dramatically increase the rate at which information can be 'written' into these devices. A conductance model using space charge limited current coupled with an electric field induced ion reconfiguration has been successfully utilized to interpret the experimentally observed transient conducting behaviors. The memory devices use the rising and falling transient current states for the storage of digital states. The magnitude of these transient currents is controlled by the magnitude and width of the write/read pulse. For the 500 nm length devices used in this work an increase in 'write' potential from 2.5 to 5.5 V decreased the time required to create a transient conductance state that can be converted into the digital signal by 50 times. This work suggests that the scaling of these devices will be favorable and that 'write' times for the conjugated polymer composite memory devices will decrease rapidly as ion driving fields increase with decreasing device size.

Electrical memory characteristics of a nondoped pi-conjugated polymer bearing carbazole moieties.

PubMed

Park, Samdae; Lee, Taek Joon; Kim, Dong Min; Kim, Jin Chul; Kim, Kyungtae; Kwon, Wonsang; Ko, Yong-Gi; Choi, Heungyeal; Chang, Taihyun; Ree, Moonhor

2010-08-19

Poly[bis(9H-carbazole-9-ethyl)dipropargylmalonate] (PCzDPM) is a novel pi-conjugated polymer bearing carbazole moieties that has been synthesized by polymerization of bis(9H-carbazole-9-ethyl)dipropargylmalonate with the aid of molybdenum chloride solution as the catalyst. This polymer is thermally stable up to 255 degrees C under a nitrogen atmosphere and 230 degrees C in air ambient; its glass-transition temperature is 147 or 128 degrees C, depending on the polymer chain conformation (helical or planar structure). The charge-transport characteristics of PCzDPM in nanometer-scaled thin films were studied as a function of temperature and film thickness. PCzDPM films with a thickness of 15-30 nm were found to exhibit very stable dynamic random access memory (DRAM) characteristics without polarity. Furthermore, the polymer films retain DRAM characteristics up to 180 degrees C. The ON-state current is dominated by Ohmic conduction, and the OFF-state current appears to undergo a transition from Ohmic to space-charge-limited conduction with a shallow-trap distribution. The ON/OFF switching of the devices is mainly governed by filament formation. The filament formation mechanism for the switching process is supported by the metallic properties of the PCzDPM film, which result in the temperature dependence of the ON-state current. In addition, the structure of this pi-conjugated polymer was found to vary with its thermal history; this change in structure can affect filament formation in the polymer film.

Damage healing ability of a shape-memory-polymer-based particulate composite with small thermoplastic contents

NASA Astrophysics Data System (ADS)

Nji, Jones; Li, Guoqiang

2012-02-01

The purpose of this study is to investigate the potential of a shape-memory-polymer (SMP)-based particulate composite to heal structural-length scale damage with small thermoplastic additive contents through a close-then-heal (CTH) self-healing scheme that was introduced in a previous study (Li and Uppu 2010 Comput. Sci. Technol. 70 1419-27). The idea is to achieve reasonable healing efficiencies with minimal sacrifice in structural load capacity. By first closing cracks, the gap between two crack surfaces is narrowed and a lesser amount of thermoplastic particles is required to achieve healing. The particulate composite was fabricated by dispersing copolyester thermoplastic particles in a shape memory polymer matrix. It is found that, for small thermoplastic contents of less than 10%, the CTH scheme followed in this study heals structural-length scale damage in the SMP particulate composite to a meaningful extent and with less sacrifice of structural capacity.

Surface engineering of ferroelectric polymer for the enhanced electrical performance of organic transistor memory

NASA Astrophysics Data System (ADS)

Kim, Do-Kyung; Lee, Gyu-Jeong; Lee, Jae-Hyun; Kim, Min-Hoi; Bae, Jin-Hyuk

2018-05-01

We suggest a viable surface control method to improve the electrical properties of organic nonvolatile memory transistors. For viable surface control, the surface of the ferroelectric insulator in the memory field-effect transistors was modified using a smooth-contact-curing process. For the modification of the ferroelectric polymer, during the curing of the ferroelectric insulators, the smooth surface of a soft elastomer contacts intimately with the ferroelectric surface. This smooth-contact-curing process reduced the surface roughness of the ferroelectric insulator without degrading its ferroelectric properties. The reduced roughness of the ferroelectric insulator increases the mobility of the organic field-effect transistor by approximately eight times, which results in a high memory on–off ratio and a low-voltage reading operation.

Implementation of a finite element analysis procedure for structural analysis of shape memory behaviour of fibre reinforced shape memory polymer composites

NASA Astrophysics Data System (ADS)

Azzawi, Wessam Al; Epaarachchi, J. A.; Islam, Mainul; Leng, Jinsong

2017-12-01

Shape memory polymers (SMPs) offer a unique ability to undergo a substantial shape deformation and subsequently recover the original shape when exposed to a particular external stimulus. Comparatively low mechanical properties being the major drawback for extended use of SMPs in engineering applications. However the inclusion of reinforcing fibres in to SMPs improves mechanical properties significantly while retaining intrinsic shape memory effects. The implementation of shape memory polymer composites (SMPCs) in any engineering application is a unique task which requires profound materials and design optimization. However currently available analytical tools have critical limitations to undertake accurate analysis/simulations of SMPC structures and slower derestrict transformation of breakthrough research outcomes to real-life applications. Many finite element (FE) models have been presented. But majority of them require a complicated user-subroutines to integrate with standard FE software packages. Furthermore, those subroutines are problem specific and difficult to use for a wider range of SMPC materials and related structures. This paper presents a FE simulation technique to model the thermomechanical behaviour of the SMPCs using commercial FE software ABAQUS. Proposed technique incorporates material time-dependent viscoelastic behaviour. The ability of the proposed technique to predict the shape fixity and shape recovery was evaluated by experimental data acquired by a bending of a SMPC cantilever beam. The excellent correlation between the experimental and FE simulation results has confirmed the robustness of the proposed technique.

Bioreducible Polymers for Therapeutic Gene Delivery

PubMed Central

Lee, Young Sook; Kim, Sung Wan

2014-01-01

Most currently available cationic polymers have significant acute toxicity concerns such as cellular toxicity, aggregation of erythrocytes, and entrapment in the lung capillary bed, largely due to their poor biocompatibility and non-degradability under physiological conditions. To develop more intelligent polymers, disulfide bonds are introduced in the design of biodegradable polymers. Herein, the sustained innovations of biomimetic nanosized constructs with bioreducible poly(disulfide amine)s demonstrate a viable clinical tool for the treatment of cardiovascular disease, anemia, diabetes, and cancer. PMID:24746626

Sequential Self-Folding Structures by 3D Printed Digital Shape Memory Polymers

NASA Astrophysics Data System (ADS)

Mao, Yiqi; Yu, Kai; Isakov, Michael S.; Wu, Jiangtao; Dunn, Martin L.; Jerry Qi, H.

2015-09-01

Folding is ubiquitous in nature with examples ranging from the formation of cellular components to winged insects. It finds technological applications including packaging of solar cells and space structures, deployable biomedical devices, and self-assembling robots and airbags. Here we demonstrate sequential self-folding structures realized by thermal activation of spatially-variable patterns that are 3D printed with digital shape memory polymers, which are digital materials with different shape memory behaviors. The time-dependent behavior of each polymer allows the temporal sequencing of activation when the structure is subjected to a uniform temperature. This is demonstrated via a series of 3D printed structures that respond rapidly to a thermal stimulus, and self-fold to specified shapes in controlled shape changing sequences. Measurements of the spatial and temporal nature of self-folding structures are in good agreement with the companion finite element simulations. A simplified reduced-order model is also developed to rapidly and accurately describe the self-folding physics. An important aspect of self-folding is the management of self-collisions, where different portions of the folding structure contact and then block further folding. A metric is developed to predict collisions and is used together with the reduced-order model to design self-folding structures that lock themselves into stable desired configurations.

Mechanical properties of shape memory polymers for morphing aircraft applications

NASA Astrophysics Data System (ADS)

Keihl, Michelle M.; Bortolin, Robert S.; Sanders, Brian; Joshi, Shiv; Tidwell, Zeb

2005-05-01

This investigation addresses basic characterization of a shape memory polymer (SMP) as a suitable structural material for morphing aircraft applications. Tests were performed for monotonic loading in high shear at constant temperature, well below, or just above the glass transition temperature. The SMP properties were time-and temperature-dependent. Recovery by the SMP to its original shape needed to be unfettered. Based on the testing SMPs appear to be an attractive and promising component in the solution for a skin material of a morphing aircraft. Their multiple state abilities allow them to easily change shape and, once cooled, resist large loads.

A Kirigami shape memory polymer honeycomb concept for deployment

NASA Astrophysics Data System (ADS)

Neville, Robin M.; Chen, Jianguo; Guo, Xiaogang; Zhang, Fenghua; Wang, Wenxin; Dobah, Yousef; Scarpa, Fabrizio; Leng, Jinsong; Peng, Hua-Xin

2017-05-01

We present a shape memory polymer (SMP) honeycomb with tuneable and shape morphing mechanical characteristics. Kirigami (Origami with cutting allowed) techniques have been used to design and manufacture the honeycomb. The cellular structure described in this work has styrene SMP hinges that create the shape change and the deployment actuation. To create a large volumetric deployment, the Kirigami open honeycomb configuration has been designed by setting an initial three-dimensional re-entrant auxetic (negative Poisson’s ratio) configuration, while the final honeycomb shape assume a convex (positive Poisson’s ratio) layout. A model was developed to predict the shape change of the structure, and compared to experimental results from a demonstrator honeycomb deployment test.

Application of graphene oxide-poly (vinyl alcohol) polymer nanocomposite for memory devices

NASA Astrophysics Data System (ADS)

Kaushal, Jyoti; Kaur, Ravneet; Sharma, Jadab; Tripathi, S. K.

2018-05-01

Significant attention has been gained by polymer nanocomposites because of their possible demands in future electronic memory devices. In the present work, device based on Graphene Oxide (GO) and polyvinyl alcohol (PVA) has been made and examined for the memory device application. The prepared Graphene oxide (GO) and GO-PVA nanocomposite (NC) has been characterized by X-ray Diffraction (XRD). GO nanosheets show the diffraction peak at 2θ = 11.60° and the interlayer spacing of 0.761 nm. The XRD of GO-PVA NC shows the diffraction peak at 2θ =18.56°. The fabricated device shows bipolar switching behavior having ON/OFF current ratio ˜102. The Write-Read-Erase-Read (WRER) cycles test shows that the Al/GO-PVA/Ag device has good stability and repeatability.

3D Printing of a Thermoplastic Shape Memory Polymer using FDM

NASA Astrophysics Data System (ADS)

Zhao, Zhiyang; Weiss, R. A.; Vogt, Bryan

Shape memory polymers (SMPs) change from a temporary shape to its permanent shape when exposed to an external stimulus. The shape memory relies on the presence of two independent networks. 3D printing provides a facile method to fabricate complex shapes with high degrees of customizability. The most common consumer 3D printing technology is fused deposition modeling (FDM), which relies on the extrusion of a thermoplastic filament to build-up the part in a layer by layer fashion. The material choices for FDM are limited, but growing. The generation of an SMP that is printable by FDM could open SMPs to many new potential applications. In this work, we demonstrate printing of thermally activated SMP using FDM. Partially neutralized poly(ethylene-co-r-methacrylic acid) ionomers (Surlyn by Dupont) was extruded into filaments and used as a model thermoplastic shape memory material. The properties of the SMP part can be readily tuned by print parameters, such as infill density or infill direction without changing the base material. We discuss the performance and characteristics of 3D printed shapes compared to their compression molded analogs.

Influence of mechanically-induced dilatation on the shape memory behavior of amorphous polymers at large deformation

NASA Astrophysics Data System (ADS)

Hanzon, Drew W.; Lu, Haibao; Yakacki, Christopher M.; Yu, Kai

2018-01-01

In this study, we explore the influence of mechanically-induced dilatation on the thermomechanical and shape memory behavior of amorphous shape memory polymers (SMPs) at large deformation. The uniaxial tension, glass transition, stress relaxation and free recovery behaviors are examined with different strain levels (up to 340% engineering strain). A multi-branched constitutive model that incorporates dilatational effects on the polymer relaxation time is established and applied to assist in discussions and understand the nonlinear viscoelastic behaviors of SMPs. It is shown that the volumetric dilatation results in an SMP network with lower viscosity, faster relaxation, and lower Tg. The influence of the dilatational effect on the thermomechanical behaviors is significant when the polymers are subject to large deformation or in a high viscosity state. The dilation also increases the free recovery rate of SMP at a given recovery temperature. Even though the tested SMPs are far beyond their linear viscoelastic region when a large programming strain is applied, the free recovery behavior still follows the time-temperature superposition (TTSP) if the dilatational effect is considered during the transformation of time scales; however, if the programming strain is different, TTSP fails in predicting the recovery behavior of SMPs because the network has different entropy state and driving force during shape recovery. Since most soft active polymers are subject to large deformation in practice, this study provides a theoretical basis to better understand their nonlinear viscoelastic behaviors, and optimize their performance in engineering applications.

Long-time dynamics of Rouse-Zimm polymers in dilute solutions with hydrodynamic memory.

PubMed

Lisy, V; Tothova, J; Zatovsky, A V

2004-12-01

The dynamics of flexible polymers in dilute solutions is studied taking into account the hydrodynamic memory, as a consequence of fluid inertia. As distinct from the Rouse-Zimm (RZ) theory, the Boussinesq friction force acts on the monomers (beads) instead of the Stokes force, and the motion of the solvent is governed by the nonstationary Navier-Stokes equations. The obtained generalized RZ equation is solved approximately using the preaveraging of the Oseen tensor. It is shown that the time correlation functions describing the polymer motion essentially differ from those in the RZ model. The mean-square displacement (MSD) of the polymer coil is at short times approximately t(2) (instead of approximately t). At long times the MSD contains additional (to the Einstein term) contributions, the leading of which is approximately t. The relaxation of the internal normal modes of the polymer differs from the traditional exponential decay. It is displayed in the long-time tails of their correlation functions, the longest lived being approximately t(-3/2) in the Rouse limit and t(-5/2) in the Zimm case, when the hydrodynamic interaction is strong. It is discussed that the found peculiarities, in particular, an effectively slower diffusion of the polymer coil, should be observable in dynamic scattering experiments. (c) 2004 American Institute of Physics

Parametric analysis and temperature effect of deployable hinged shells using shape memory polymers

NASA Astrophysics Data System (ADS)

Tao, Ran; Yang, Qing-Sheng; He, Xiao-Qiao; Liew, Kim-Meow

2016-11-01

Shape memory polymers (SMPs) are a class of intelligent materials, which are defined by their capacity to store a temporary shape and recover an original shape. In this work, the shape memory effect of SMP deployable hinged shell is simulated by using compiled user defined material subroutine (UMAT) subroutine of ABAQUS. Variations of bending moment and strain energy of the hinged shells with different temperatures and structural parameters in the loading process are given. The effects of the parameters and temperature on the nonlinear deformation process are emphasized. The entire thermodynamic cycle of SMP deployable hinged shell includes loading at high temperature, load carrying with cooling, unloading at low temperature and recovering the original shape with heating. The results show that the complicated thermo-mechanical deformation and shape memory effect of SMP deployable hinge are influenced by the structural parameters and temperature. The design ability of SMP smart hinged structures in practical application is prospected.

Ultra Low Density Shape Memory Polymer Foams With Tunable Physicochemical Properties for Treatment of intracranial Aneurysms

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singhal, Pooja

Shape memory polymers (SMPs) are a rapidly emerging class of smart materials that can be stored in a deformed temporary shape, and can actively return to their original shape upon application of an external stimulus such as heat, pH or light. This behavior is particularly advantageous for minimally invasive biomedical applications comprising embolic/regenerative scaffolds, as it enables a transcatheter delivery of the device to the target site. The focus of this work was to exploit this shape memory behavior of polyurethanes, and develop an efficient embolic SMP foam device for the treatment of intracranial aneurysms.In summary, this work reports amore » novel family of ultra low density polymer foams which can be delivered via a minimally invasive surgery to the aneurysm site, actuated in a controlled manner to efficiently embolize the aneurysm while promoting physiological fluid/blood flow through the reticulated/open porous structure, and eventually biodegrade leading to complete healing of the vasculature.« less

Self-Assembled ROS-Sensitive Polymer-Peptide Therapeutics Incorporating Built-in Reporters for Evaluation of Treatment Efficacy.

PubMed

Qiao, Zeng-Ying; Zhao, Wen-Jing; Cong, Yong; Zhang, Di; Hu, Zhiyuan; Duan, Zhong-Yu; Wang, Hao

2016-05-09

One of the major challenges in current cancer therapy is to maximize therapeutic effect and evaluate tumor progression under the scheduled treatment protocol. To address these challenges, we synthesized the cytotoxic peptide (KLAKLAK)2 (named KLAK) conjugated amphiphilic poly(β-thioester)s copolymers (H-P-K) composed of reactive oxygen species (ROS) sensitive backbones and hydrophilic polyethylene glycol (PEG) side chains. H-P-K could self-assemble into micelle-like nanoparticles by hydrophobic interaction with copolymer backbones as cores and PEG and KLAK as shells. The assembled polymer-peptide nanoparticles remarkably improved cellular internalization and accumulation of therapeutic KLAK in cells. Compared to free KLAK peptide, the antitumor activity of H-P-K was significantly enhanced up to ∼400 times, suggesting the effectiveness of the nanoscaled polymer-peptide conjugation as biopharmaceuticals. The higher antitumor activity of nanoparticles was attributed to the efficient disruption of mitochondrial membranes and subsequent excessive ROS production in cells. To realize the ROS monitoring and treatment evaluation, we encapsulated squaraine (SQ) dyes as built-in reporters in ROS-sensitive H-P-K micelles. The overgenerated ROS around mitochondria stimulated the swelling of nanoparticles and subsequent release of SQ, which formed H-aggregates and significantly increased the photoacoustic (PA) signal. We believed that this self-assembled polymer-peptide nanotherapeutics incorporating built-in reporters has great potential for high antitumor performance and in situ treatment evaluation.

Advanced functional polymers for regenerative and therapeutic dentistry.

PubMed

Lai, W-F; Oka, K; Jung, H-S

2015-07-01

Use of ceramics and polymers continues to dominate clinical procedures in modern dentistry. Polymers have provided the basis for adhesives, tissue void fillers, and artificial replacements for whole teeth. They have been remarkably effective in the clinic at restoration of major dental functions after damage or loss of teeth. With the rapid development of polymer science, dental materials science has significantly lagged behind in harnessing these advanced polymer products. What they offer is new and unique properties superior to traditional polymers and crucially a range of properties that more closely match natural biomaterials. Therefore, we should pursue more vigorously the benefits of advanced polymers in dentistry. In this review, we highlight how the latest generation of advanced polymers will enhance the application of materials in the dental clinic using numerous promising examples. Polymers have a broad range of applications in modern dentistry. Some major applications are to construct frameworks that mimic the precise structure of tissues, to restore tooth organ function, and to deliver bioactive agents to influence cell behavior from the inside. The future of polymers in dentistry must include all these new enhancements to increase biological and clinical effectiveness beyond what can be achieved with traditional biomaterials. © 2014 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

MACROMOLECULAR THERAPEUTICS

PubMed Central

Yang, Jiyuan; Kopeček, Jindřich

2014-01-01

This review covers water-soluble polymer-drug conjugates and macromolecules that possess biological activity without attached low molecular weight drugs. The main design principles of traditional and backbone degradable polymer-drug conjugates as well as the development of a new paradigm in nanomedicines – (low molecular weight) drug-free macromolecular therapeutics are discussed. To address the biological features of cancer, macromolecular therapeutics directed to stem/progenitor cells and the tumor microenvironment are deliberated. Finally, the future perspectives of the field are briefly debated. PMID:24747162

High Performance Transparent Transistor Memory Devices Using Nano-Floating Gate of Polymer/ZnO Nanocomposites

NASA Astrophysics Data System (ADS)

Shih, Chien-Chung; Lee, Wen-Ya; Chiu, Yu-Cheng; Hsu, Han-Wen; Chang, Hsuan-Chun; Liu, Cheng-Liang; Chen, Wen-Chang

2016-02-01

Nano-floating gate memory devices (NFGM) using metal nanoparticles (NPs) covered with an insulating polymer have been considered as a promising electronic device for the next-generation nonvolatile organic memory applications NPs. However, the transparency of the device with metal NPs is restricted to 60~70% due to the light absorption in the visible region caused by the surface plasmon resonance effects of metal NPs. To address this issue, we demonstrate a novel NFGM using the blends of hole-trapping poly (9-(4-vinylphenyl) carbazole) (PVPK) and electron-trapping ZnO NPs as the charge storage element. The memory devices exhibited a remarkably programmable memory window up to 60 V during the program/erase operations, which was attributed to the trapping/detrapping of charge carriers in ZnO NPs/PVPK composite. Furthermore, the devices showed the long-term retention time (>105 s) and WRER test (>200 cycles), indicating excellent electrical reliability and stability. Additionally, the fabricated transistor memory devices exhibited a relatively high transparency of 90% at the wavelength of 500 nm based on the spray-coated PEDOT:PSS as electrode, suggesting high potential for transparent organic electronic memory devices.

Microfabricated therapeutic actuators

DOEpatents

Lee, Abraham P.; Northrup, M. Allen; Ciarlo, Dino R.; Krulevitch, Peter A.; Benett, William J.

1999-01-01

Microfabricated therapeutic actuators are fabricated using a shape memory polymer (SMP), a polyurethane-based material that undergoes a phase transformation at a specified temperature (Tg). At a temperature above temperature Tg material is soft and can be easily reshaped into another configuration. As the temperature is lowered below temperature Tg the new shape is fixed and locked in as long as the material stays below temperature Tg. Upon reheating the material to a temperature above Tg, the material will return to its original shape. By the use of such SMP material, SMP microtubing can be used as a release actuator for the delivery of embolic coils through catheters into aneurysms, for example. The microtubing can be manufactured in various sizes and the phase change temperature Tg is determinate for an intended temperature target and intended use.

Microfabricated therapeutic actuators

DOEpatents

Lee, A.P.; Northrup, M.A.; Ciarlo, D.R.; Krulevitch, P.A.; Benett, W.J.

1999-06-15

Microfabricated therapeutic actuators are fabricated using a shape memory polymer (SMP), a polyurethane-based material that undergoes a phase transformation at a specified temperature (Tg). At a temperature above temperature Tg material is soft and can be easily reshaped into another configuration. As the temperature is lowered below temperature Tg the new shape is fixed and locked in as long as the material stays below temperature Tg. Upon reheating the material to a temperature above Tg, the material will return to its original shape. By the use of such SMP material, SMP microtubing can be used as a release actuator for the delivery of embolic coils through catheters into aneurysms, for example. The microtubing can be manufactured in various sizes and the phase change temperature Tg is determinate for an intended temperature target and intended use. 8 figs.

Macromolecular therapeutics.

PubMed

Yang, Jiyuan; Kopeček, Jindřich

2014-09-28

This review covers water-soluble polymer-drug conjugates and macromolecules that possess biological activity without attached low molecular weight drugs. The main design principles of traditional and backbone degradable polymer-drug conjugates as well as the development of a new paradigm in nanomedicines - (low molecular weight) drug-free macromolecular therapeutics are discussed. To address the biological features of cancer, macromolecular therapeutics directed to stem/progenitor cells and the tumor microenvironment are deliberated. Finally, the future perspectives of the field are briefly debated. Copyright © 2014 Elsevier B.V. All rights reserved.

Advancing reversible shape memory by tuning the polymer network architecture

DOE PAGES

Li, Qiaoxi; Zhou, Jing; Vatankhah-Varnoosfaderani, Mohammad; ...

2016-02-02

Because of counteraction of a chemical network and a crystalline scaffold, semicrystalline polymer networks exhibit a peculiar behavior—reversible shape memory (RSM), which occurs naturally without applying any external force and particular structural design. There are three RSM properties: (i) range of reversible strain, (ii) rate of strain recovery, and (iii) decay of reversibility with time, which can be improved by tuning the architecture of the polymer network. Different types of poly(octylene adipate) networks were synthesized, allowing for control of cross-link density and network topology, including randomly cross-linked network by free-radical polymerization, thiol–ene clicked network with enhanced mesh uniformity, and loosemore » network with deliberately incorporated dangling chains. It is shown that the RSM properties are controlled by average cross-link density and crystal size, whereas topology of a network greatly affects its extensibility. In conclusion, we have achieved 80% maximum reversible range, 15% minimal decrease in reversibility, and fast strain recovery rate up to 0.05 K –1, i.e., ca. 5% per 10 s at a cooling rate of 5 K/min.« less

Highly reliable top-gated thin-film transistor memory with semiconducting, tunneling, charge-trapping, and blocking layers all of flexible polymers.

PubMed

Wang, Wei; Hwang, Sun Kak; Kim, Kang Lib; Lee, Ju Han; Cho, Suk Man; Park, Cheolmin

2015-05-27

The core components of a floating-gate organic thin-film transistor nonvolatile memory (OTFT-NVM) include the semiconducting channel layer, tunneling layer, floating-gate layer, and blocking layer, besides three terminal electrodes. In this study, we demonstrated OTFT-NVMs with all four constituent layers made of polymers based on consecutive spin-coating. Ambipolar charges injected and trapped in a polymer electret charge-controlling layer upon gate program and erase field successfully allowed for reliable bistable channel current levels at zero gate voltage. We have observed that the memory performance, in particular the reliability of a device, significantly depends upon the thickness of both blocking and tunneling layers, and with an optimized layer thickness and materials selection, our device exhibits a memory window of 15.4 V, on/off current ratio of 2 × 10(4), read and write endurance cycles over 100, and time-dependent data retention of 10(8) s, even when fabricated on a mechanically flexible plastic substrate.

Potential Therapeutics for Vascular Cognitive Impairment and Dementia.

PubMed

Sun, Miao-Kun

2017-10-16

As the human lifespan increases, the number of people affected by age-related dementia is growing at an epidemic pace. Vascular pathology dramatically affects cognitive profiles, resulting in dementia and cognitive impairment. While vascular dementia itself constitutes a medical challenge, hypoperfusion/vascular risk factors enhance amyloid toxicity and other memory-damaging factors and hasten Alzheimer's disease (AD) and other memory disorders' progression, as well as negatively affect treatment outcome. Few therapeutic options are, however, currently available to improve the prognosis of patients with vascular dementia and cognitive impairment, mixed AD dementia with vascular pathology, or other memory disorders. Emerging evidence, however, indicates that, like AD and other memory disorders, synaptic impairment underlies much of the memory impairment in the cognitive decline of vascular cognitive impairment and vascular dementia. Effective rescues of the memory functions might be achieved through synaptic and memory therapeutics, targeting distinct molecular signaling pathways that support the formation of new synapses and maintaining their connections. Potential therapeutic agents include: 1) memory therapeutic agents that rescue synaptic and memory functions after the brain insults; 2) anti-pathologic therapeutics and an effective management of vascular risk factors; and 3) preventative therapeutic agents that achieve memory therapy through functional enhancement. Their development and potential as clinically effective memory therapeutics for vascular cognitive impairment and dementia are discussed in this review. These therapeutic agents are also likely to benefit patients with AD and/or other types of memory disorders. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

An approach to predict the shape-memory behavior of amorphous polymers from Dynamic Mechanical Analysis (DMA) data

NASA Astrophysics Data System (ADS)

Kuki, Ákos; Czifrák, Katalin; Karger-Kocsis, József; Zsuga, Miklós; Kéki, Sándor

2015-02-01

The prediction of shape-memory behavior is essential regarding the design of a smart material for different applications. This paper proposes a simple and quick method for the prediction of shape-memory behavior of amorphous shape memory polymers (SMPs) on the basis of a single dynamic mechanical analysis (DMA) temperature sweep at constant frequency. All the parameters of the constitutive equations for linear viscoelasticity are obtained by fitting the DMA curves. The change with the temperature of the time-temperature superposition shift factor ( a T ) is expressed by the Williams-Landel-Ferry (WLF) model near and above the glass transition temperature ( T g ), and by the Arrhenius law below T g . The constants of the WLF and Arrhenius equations can also be determined. The results of our calculations agree satisfactorily with the experimental free recovery curves from shape-memory tests.

Formation of biodegradated polymers as components of future composite materials on the basis of shape memory alloy of medical appointment

NASA Astrophysics Data System (ADS)

Nasakina, E. O.; Baikin, A. S.; Sergiyenko, K. V.; Kaplan, M. A.; Konushkin, S. V.; Yakubov, A. D.; Izvin, A. V.; Sudarchikova, M. A.; Sevost’yanov, M. A.; Kolmakov, A. G.

2018-04-01

The processes of formation of polymer polylactide or polyglycylidactide films for the subsequent creation of a layered composite with a biodegradable layer on the basis of a nickel-free shape memory alloy TiNbTaZr are studied. The structure of the samples was determined using an SEM. The correspondence of morphology of surfaces of and the substrate itself is noted. High adhesion of the polymer to the future basis of the developed composite material is supposed. The formed films is homogeneous and amorphous throughout the polymer volume. By varying the volume of solutions, it is possible to obtain films of a given thickness for any type of polymer, its molecular weight, and the solution concentration of the polymer in chloroform. Poly (glycolide-lactide) should be more plastic than polylactide.

Ultra low density biodegradable shape memory polymer foams with tunable physical properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singhal, Pooja; Wilson, Thomas S.; Cosgriff-Hernandez, Elizabeth

Compositions and/or structures of degradable shape memory polymers (SMPs) ranging in form from neat/unfoamed to ultra low density materials of down to 0.005 g/cc density. These materials show controllable degradation rate, actuation temperature and breadth of transitions along with high modulus and excellent shape memory behavior. A method of m ly low density foams (up to 0.005 g/cc) via use of combined chemical and physical aking extreme blowing agents, where the physical blowing agents may be a single compound or mixtures of two or more compounds, and other related methods, including of using multiple co-blowing agents of successively higher boilingmore » points in order to achieve a large range of densities for a fixed net chemical composition. Methods of optimization of the physical properties of the foams such as porosity, cell size and distribution, cell openness etc. of these materials, to further expand their uses and improve their performance.« less

Coarse-grained simulation of molecular mechanisms of recovery in thermally activated shape-memory polymers

NASA Astrophysics Data System (ADS)

Abberton, Brendan C.; Liu, Wing Kam; Keten, Sinan

2013-12-01

Thermally actuated shape-memory polymers (SMPs) are capable of being programmed into a temporary shape and then recovering their permanent reference shape upon exposure to heat, which facilitates a phase transition that allows dramatic increase in molecular mobility. Experimental, analytical, and computational studies have established empirical relations of the thermomechanical behavior of SMPs that have been instrumental in device design. However, the underlying mechanisms of the recovery behavior and dependence on polymer microstructure remain to be fully understood for copolymer systems. This presents an opportunity for bottom-up studies through molecular modeling; however, the limited time-scales of atomistic simulations prohibit the study of key performance metrics pertaining to recovery. In order to elucidate the effects of phase fraction, recovery temperature, and deformation temperature on shape recovery, here we investigate the shape-memory behavior in a copolymer model with coarse-grained potentials using a two-phase molecular model that reproduces physical crosslinking. Our simulation protocol allows observation of upwards of 90% strain recovery in some cases, at time-scales that are on the order of the timescale of the relevant relaxation mechanism (stress relaxation in the unentangled soft-phase). Partial disintegration of the glassy phase during mechanical deformation is found to contribute to irrecoverable strain. Temperature dependence of the recovery indicates nearly full elastic recovery above the trigger temperature, which is near the glass-transition temperature of the rubbery switching matrix. We find that the trigger temperature is also directly correlated with the deformation temperature, indicating that deformation temperature influences the recovery temperatures required to obtain a given amount of shape recovery, until the plateau regions overlap above the transition region. Increasing the fraction of glassy phase results in higher strain

Preparation and characterization of shape memory polymer scaffolds via solvent casting/particulate leaching.

PubMed

De Nardo, Luigi; Bertoldi, Serena; Cigada, Alberto; Tanzi, Maria Cristina; Haugen, Håvard Jostein; Farè, Silvia

2012-09-27

Porous Shape Memory Polymers (SMPs) are ideal candidates for the fabrication of defect fillers, able to support tissue regeneration via minimally invasive approaches. In this regard, control of pore size, shape and interconnection is required to achieve adequate nutrient transport and cell ingrowth. Here, we assessed the feasibility of the preparation of SMP porous structures and characterized their chemico-physical properties and in vitro cell response. SMP scaffolds were obtained via solvent casting/particulate leaching of gelatin microspheres, prepared via oil/water emulsion. A solution of commercial polyether-urethane (MM-4520, Mitsubishi Heavy Industries) was cast on compacted microspheres and leached-off after polymer solvent evaporation. The obtained structures were characterized in terms of morphology (SEM and micro-CT), thermo-mechanical properties (DMTA), shape recovery behavior in compression mode, and in vitro cytocompatibility (MG63 Osteoblast-like cell line). The fabrication process enabled easy control of scaffold morphology, pore size, and pore shape by varying the gelatin microsphere morphology. Homogeneous spherical and interconnected pores have been achieved together with the preservation of shape memory ability, with recovery rate up to 90%. Regardless of pore dimensions, MG63 cells were observed adhering and spreading onto the inner surface of the scaffolds obtained for up to seven days of static in vitro tests. A new class of SMP porous structures has been obtained and tested in vitro: according to these preliminary results reported, SMP scaffolds can be further exploited in the design of a new class of implantable devices.

Triple shape memory polymers by 4D printing

NASA Astrophysics Data System (ADS)

Bodaghi, M.; Damanpack, A. R.; Liao, W. H.

2018-06-01

This article aims at introducing triple shape memory polymers (SMPs) by four-dimensional (4D) printing technology and shaping adaptive structures for mechanical/bio-medical devices. The main approach is based on arranging hot–cold programming of SMPs with fused decomposition modeling technology to engineer adaptive structures with triple shape memory effect (SME). Experiments are conducted to characterize elasto-plastic and hyper-elastic thermo-mechanical material properties of SMPs in low and high temperatures at large deformation regime. The feasibility of the dual and triple SMPs with self-bending features is demonstrated experimentally. It is advantageous in situations either where it is desired to perform mechanical manipulations on the 4D printed objects for specific purposes or when they experience cold programming inevitably before activation. A phenomenological 3D constitutive model is developed for quantitative understanding of dual/triple SME of SMPs fabricated by 4D printing in the large deformation range. Governing equations of equilibrium are established for adaptive structures on the basis of the nonlinear Green–Lagrange strains. They are then solved by developing a finite element approach along with an elastic-predictor plastic-corrector return map procedure accomplished by the Newton–Raphson method. The computational tool is applied to simulate dual/triple SMP structures enabled by 4D printing and explore hot–cold programming mechanisms behind material tailoring. It is shown that the 4D printed dual/triple SMPs have great potential in mechanical/bio-medical applications such as self-bending gripers/stents and self-shrinking/tightening staples.

PCL-based Shape Memory Polymers with Variable PDMS Soft Segment Lengths

PubMed Central

Zhang, Dawei; Giese, Melissa L.; Prukop, Stacy L.; Grunlan, Melissa A.

2012-01-01

Thermoresponsive shape memory polymers (SMPs) are stimuli-responsive materials that return to their permanent shape from a temporary shape in response to heating. The design of new SMPs which obtain a broader range of properties including mechanical behavior is critical to realize their potential in biomedical as well as industrial and aerospace applications. To tailor the properties of SMPs, “AB networks” comprised of two distinct polymer components have been investigated but are overwhelmingly limited to those in which both components are organic. In this present work, we prepared inorganic-organic SMPs comprised of inorganic polydimethyl-siloxane (PDMS) segments of varying lengths and organic poly(ε-caprolactone) (PCL) segments. PDMS has a particularly low Tg (−125 °C) which makes it a particularly effective soft segment to tailor the mechanical properties of PCL-based SMPs. The SMPs were prepared via the rapid photocure of solutions of diacrylated PCL40-block-PDMSm-block-PCL40 macromers (m = 20, 37, 66 and 130). The resulting inorganic-organic SMP networks exhibited excellent shape fixity and recovery. By changing the PDMS segment length, the thermal, mechanical, and surface properties were systematically altered. PMID:22904597

Fire-Retardant, Self-Extinguishing Inorganic/Polymer Composite Memory Foams.

PubMed

Chatterjee, Soumyajyoti; Shanmuganathan, Kadhiravan; Kumaraswamy, Guruswamy

2017-12-27

Polymeric foams used in furniture and automotive and aircraft seating applications rely on the incorporation of environmentally hazardous fire-retardant additives to meet fire safety norms. This has occasioned significant interest in novel approaches to the elimination of fire-retardant additives. Foams based on polymer nanocomposites or based on fire-retardant coatings show compromised mechanical performance and require additional processing steps. Here, we demonstrate a one-step preparation of a fire-retardant ice-templated inorganic/polymer hybrid that does not incorporate fire-retardant additives. The hybrid foams exhibit excellent mechanical properties. They are elastic to large compressional strain, despite the high inorganic content. They also exhibit tunable mechanical recovery, including viscoelastic "memory". These hybrid foams are prepared using ice-templating that relies on a green solvent, water, as a porogen. Because these foams are predominantly comprised of inorganic components, they exhibit exceptional fire retardance in torch burn tests and are self-extinguishing. After being subjected to a flame, the foam retains its porous structure and does not drip or collapse. In micro-combustion calorimetry, the hybrid foams show a peak heat release rate that is only 25% that of a commercial fire-retardant polyurethanes. Finally, we demonstrate that we can use ice-templating to prepare hybrid foams with different inorganic colloids, including cheap commercial materials. We also demonstrate that ice-templating is amenable to scale up, without loss of mechanical performance or fire-retardant properties.

A Thrombus Generation Model Applied to Aneurysms Treated with Shape Memory Polymer Foam and Metal Coils

NASA Astrophysics Data System (ADS)

Horn, John; Ortega, Jason; Hartman, Jonathan; Maitland, Duncan

2015-11-01

To prevent their rupture, intracranial aneurysms are often treated with endovascular metal coils which fill the aneurysm sac and isolate it from the arterial flow. Despite its widespread use, this method can result in suboptimal outcomes leading to aneurysm recurrence. Recently, shape memory polymer foam has been proposed as an alternative aneurysm filler. In this work, a computational model has been developed to predict thrombus formation in blood in response to such cardiovascular implantable devices. The model couples biofluid and biochemical phenomena present as the blood interacts with a device and stimulates thrombus formation. This model is applied to simulations of both metal coil and shape memory polymer foam treatments within an idealized 2D aneurysm geometry. Using the predicted thrombus responses, the performance of these treatments is evaluated and compared. The results suggest that foam-treated aneurysms may fill more quickly and more completely with thrombus than coil-filled aneurysms, potentially leading to improved long-term aneurysm healing. This work was performed in part under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.

Reconfigurable Photonic Crystals Enabled by Multistimuli-Responsive Shape Memory Polymers Possessing Room Temperature Shape Processability.

PubMed

Fang, Yin; Leo, Sin-Yen; Ni, Yongliang; Wang, Junyu; Wang, Bingchen; Yu, Long; Dong, Zhe; Dai, Yuqiong; Basile, Vito; Taylor, Curtis; Jiang, Peng

2017-02-15

Traditional shape memory polymers (SMPs) are mostly thermoresponsive, and their applications in nano-optics are hindered by heat-demanding programming and recovery processes. By integrating a polyurethane-based shape memory copolymer with templating nanofabrication, reconfigurable/rewritable macroporous photonic crystals have been demonstrated. This SMP coupled with the unique macroporous structure enables unusual all-room-temperature shape memory cycles. "Cold" programming involving microscopic order-disorder transitions of the templated macropores is achieved by mechanically deforming the macroporous SMP membranes. The rapid recovery of the permanent, highly ordered photonic crystal structure from the temporary, disordered configuration can be triggered by multiple stimuli including a large variety of vapors and solvents, heat, and microwave radiation. Importantly, the striking chromogenic effects associated with these athermal and thermal processes render a sensitive and noninvasive optical methodology for quantitatively characterizing the intriguing nanoscopic shape memory effects. Some critical parameters/mechanisms that could significantly affect the final performance of SMP-based reconfigurable photonic crystals including strain recovery ratio, dynamics and reversibility of shape recovery, as well as capillary condensation of vapors in macropores, which play a crucial role in vapor-triggered recovery, can be evaluated using this new optical technology.

Feasibility study of polyurethane shape-memory polymer actuators for pressure bandage application

PubMed Central

Ahmad, Manzoor; Luo, Jikui; Miraftab, Mohsen

2012-01-01

The feasibility of laboratory-synthesized polyurethane-based shape-memory polymer (SMPU) actuators has been investigated for possible application in medical pressure bandages where gradient pressure is required between the ankle and the knee for treatment of leg ulcers. In this study, using heat as the stimulant, SMPU strip actuators have been subjected to gradual and cyclic stresses; their recovery force, reproducibility and reusability have been monitored with respect to changes in temperature and circumference of a model leg, and the stress relaxation at various temperatures has been investigated. The findings suggest that SMPU actuators can be used for the development of the next generation of pressure bandages. PMID:27877473

Feasibility study of polyurethane shape-memory polymer actuators for pressure bandage application.

PubMed

Ahmad, Manzoor; Luo, Jikui; Miraftab, Mohsen

2012-02-01

The feasibility of laboratory-synthesized polyurethane-based shape-memory polymer (SMPU) actuators has been investigated for possible application in medical pressure bandages where gradient pressure is required between the ankle and the knee for treatment of leg ulcers. In this study, using heat as the stimulant, SMPU strip actuators have been subjected to gradual and cyclic stresses; their recovery force, reproducibility and reusability have been monitored with respect to changes in temperature and circumference of a model leg, and the stress relaxation at various temperatures has been investigated. The findings suggest that SMPU actuators can be used for the development of the next generation of pressure bandages.

Biodegradable toughened nanohybrid shape memory polymer for smart biomedical applications.

PubMed

Biswas, Arpan; Singh, Akhand Pratap; Rana, Dipak; Aswal, Vinod K; Maiti, Pralay

2018-05-31

A polyurethane nanohybrid has been prepared through the in situ polymerization of an aliphatic diisocyanate, ester polyol and a chain extender in the presence of two-dimensional platelets. Polymerization within the platelet galleries helps to intercalate, generate diverse nanostructure and improve the nano to macro scale self-assembly, which leads to a significant enhancement in the toughness and thermal stability of the nanohybrid in comparison to pure polyurethane. The extensive interactions, the reason for property enhancement, between nanoplatelets and polymer chains are revealed through spectroscopic measurements and thermal studies. The nanohybrid exhibits significant improvement in the shape memory phenomena (91% recovery) at the physiological temperature, which makes it suitable for many biomedical applications. The structural alteration, studied through temperature dependent small angle neutron scattering and X-ray diffraction, along with unique crystallization behavior have extensively revealed the special shape memory behavior of this nanohybrid and facilitated the understanding of the molecular flipping in the presence of nanoplatelets. Cell line studies and subsequent imaging testify that this nanohybrid is a superior biomaterial that is suitable for use in the biomedical arena. In vivo studies on albino rats exhibit the potential of the shape memory effect of the nanohybrid as a self-tightening suture in keyhole surgery by appropriately closing the lips of the wound through the recovery of the programmed shape at physiological temperature with faster healing of the wound and without the formation of any scar. Further, the improved biodegradable nature along with the rapid self-expanding ability of the nanohybrid at 37 °C make it appropriate for many biomedical applications including a self-expanding stent for occlusion recovery due to its tough and flexible nature.

Variable stiffness corrugated composite structure with shape memory polymer for morphing skin applications

NASA Astrophysics Data System (ADS)

Gong, Xiaobo; Liu, Liwu; Scarpa, Fabrizio; Leng, Jinsong; Liu, Yanju

2017-03-01

This work presents a variable stiffness corrugated structure based on a shape memory polymer (SMP) composite with corrugated laminates as reinforcement that shows smooth aerodynamic surface, extreme mechanical anisotropy and variable stiffness for potential morphing skin applications. The smart composite corrugated structure shows a low in-plane stiffness to minimize the actuation energy, but also possess high out-of-plane stiffness to transfer the aerodynamic pressure load. The skin provides an external smooth aerodynamic surface because of the one-sided filling with the SMP. Due to variable stiffness of the shape memory polymer the morphing skin exhibits a variable stiffness with a change of temperature, which can help the skin adjust its stiffness according different service environments and also lock the temporary shape without external force. Analytical models related to the transverse and bending stiffness are derived and validated using finite element techniques. The stiffness of the morphing skin is further investigated by performing a parametric analysis against the geometry of the corrugation and various sets of SMP fillers. The theoretical and numerical models show a good agreement and demonstrate the potential of this morphing skin concept for morphing aircraft applications. We also perform a feasibility study of the use of this morphing skin in a variable camber morphing wing baseline. The results show that the morphing skin concept exhibits sufficient bending stiffness to withstand the aerodynamic load at low speed (less than 0.3 Ma), while demonstrating a large transverse stiffness variation (up to 191 times) that helps to create a maximum mechanical efficiency of the structure under varying external conditions.

A Structural Approach to Establishing a Platform Chemistry for the Tunable, Bulk Electron Beam Cross-Linking of Shape Memory Polymer Systems

PubMed Central

Hearon, Keith; Besset, Celine J.; Lonnecker, Alexander T.; Ware, Taylor; Voit, Walter E.; Wilson, Thomas S.; Wooley, Karen L.; Maitland, Duncan J.

2014-01-01

The synthetic design and thermomechanical characterization of shape memory polymers (SMPs) built from a new polyurethane chemistry that enables facile, bulk and tunable cross-linking of low-molecular weight thermoplastics by electron beam irradiation is reported in this study. SMPs exhibit stimuli-induced geometry changes and are being proposed for applications in numerous fields. We have previously reported a polyurethane SMP system that exhibits the complex processing capabilities of thermoplastic polymers and the mechanical robustness and tunability of thermomechanical properties that are often characteristic of thermoset materials. These previously reported polyurethanes suffer practically because the thermoplastic molecular weights needed to achieve target cross-link densities severely limit high-throughput thermoplastic processing and because thermally unstable radiation-sensitizing additives must be used to achieve high enough cross-link densities to enable desired tunable shape memory behavior. In this study, we demonstrate the ability to manipulate cross-link density in low-molecular weight aliphatic thermoplastic polyurethane SMPs (Mw as low as ~1.5 kDa) without radiation-sensitizing additives by incorporating specific structural motifs into the thermoplastic polymer side chains that we hypothesized would significantly enhance susceptibility to e-beam cross-linking. A custom diol monomer was first synthesized and then implemented in the synthesis of neat thermoplastic polyurethane SMPs that were irradiated at doses ranging from 1 to 500 kGy. Dynamic mechanical analysis (DMA) demonstrated rubbery moduli to be tailorable between 0.1 and 55 MPa, and both DMA and sol/gel analysis results provided fundamental insight into our hypothesized mechanism of electron beam cross-linking, which enables controllable bulk cross-linking to be achieved in highly processable, low-molecular weight thermoplastic shape memory polymers without sensitizing additives. PMID

Synthesis of ZnO nanorods and observation of resistive switching memory in ZnO based polymer nanocomposites

NASA Astrophysics Data System (ADS)

Nair, Manjula G.; Malakar, Meenakshi; Mohapatra, Saumya R.; Chowdhury, Avijit

2018-05-01

This research reports the observation of bipolar resistive switching memory in ZnO nanorod based polymer nanocomposites. We synthesized ZnO nanorods by wet-chemical method and characterized them using XRD, UV-VIS spectroscopy and SEM. The synthesized materials have hexagonal ZnO phase with grain size of 24 nm and having strong orientation along (101) direction as observed from XRD. The SEM micrograph confirms the formation of ZnO nanorods with diameter in the range of 10 to 20 nm and length of the order of 1 µm. From optical absorption spectra the band gap is estimated to be 2.42 eV. ZnO nanorods were dispersed in PVDF-HFP polymer matrix to prepare the nanocomposite. This nanocomposite was used as active layer in the devices having sandwich structure of ITO/PVDF-HFP+ZnO nanorods/Al. Bipolar non-volatile memory was observed with ON-OFF resistance ratio of the order of 103 and with a wide voltage window of 2.3V. The switching mechanism could be due to the trapping and de-trapping of electrons by the ZnO nanorods in the nanocomposite during ON and OFF states respectively.

Nanoscale Design of Nano-Sized Particles in Shape-Memory Polymer Nanocomposites Driven by Electricity

PubMed Central

Lu, Haibao; Huang, Wei Min; Liang, Fei; Yu, Kai

2013-01-01

In the last few years, we have witnessed significant progress in developing high performance shape memory polymer (SMP) nanocomposites, in particular, for shape recovery activated by indirect heating in the presence of electricity, magnetism, light, radio frequency, microwave and radiation, etc. In this paper, we critically review recent findings in Joule heating of SMP nanocomposites incorporated with nanosized conductive electromagnetic particles by means of nanoscale control via applying an electro- and/or magnetic field. A few different nanoscale design principles to form one-/two-/three- dimensional conductive networks are discussed. PMID:28788303

Polymers for Drug Delivery Systems

PubMed Central

Liechty, William B.; Kryscio, David R.; Slaughter, Brandon V.; Peppas, Nicholas A.

2012-01-01

Polymers have played an integral role in the advancement of drug delivery technology by providing controlled release of therapeutic agents in constant doses over long periods, cyclic dosage, and tunable release of both hydrophilic and hydrophobic drugs. From early beginnings using off-the-shelf materials, the field has grown tremendously, driven in part by the innovations of chemical engineers. Modern advances in drug delivery are now predicated upon the rational design of polymers tailored for specific cargo and engineered to exert distinct biological functions. In this review, we highlight the fundamental drug delivery systems and their mathematical foundations and discuss the physiological barriers to drug delivery. We review the origins and applications of stimuli-responsive polymer systems and polymer therapeutics such as polymer-protein and polymer-drug conjugates. The latest developments in polymers capable of molecular recognition or directing intracellular delivery are surveyed to illustrate areas of research advancing the frontiers of drug delivery. PMID:22432577

Fabrication and characterization of cylindrical light diffusers comprised of shape memory polymer.

PubMed

Small, Ward; Buckley, Patrick R; Wilson, Thomas S; Loge, Jeffrey M; Maitland, Kristen D; Maitland, Duncan J

2008-01-01

We developed a technique for constructing light diffusing devices comprised of a flexible shape memory polymer (SMP) cylindrical diffuser attached to the tip of an optical fiber. The devices are fabricated by casting an SMP rod over the cleaved tip of an optical fiber and media blasting the SMP rod to create a light diffusing surface. The axial and polar emission profiles and circumferential (azimuthal) uniformity are characterized for various blasting pressures, nozzle-to-sample distances, and nozzle translation speeds. The diffusers are generally strongly forward-directed and consistently withstand over 8 W of incident IR laser light without suffering damage when immersed in water. These devices are suitable for various endoluminal and interstitial biomedical applications.

Fabrication and characterization of cylindrical light diffusers comprised of shape memory polymer

PubMed Central

Small, Ward; Buckley, Patrick R.; Wilson, Thomas S.; Loge, Jeffrey M.; Maitland, Kristen D.; Maitland, Duncan J.

2009-01-01

We developed a technique for constructing light diffusing devices comprised of a flexible shape memory polymer (SMP) cylindrical diffuser attached to the tip of an optical fiber. The devices are fabricated by casting an SMP rod over the cleaved tip of an optical fiber and media blasting the SMP rod to create a light diffusing surface. The axial and polar emission profiles and circumferential (azimuthal) uniformity are characterized for various blasting pressures, nozzle-to-sample distances, and nozzle translation speeds. The diffusers are generally strongly forward-directed and consistently withstand over 8 W of incident IR laser light without suffering damage when immersed in water. These devices are suitable for various endoluminal and interstitial biomedical applications. PMID:18465981

The impact of shape memory test on degradation profile of a bioresorbable polymer.

PubMed

Musioł, Marta; Jurczyk, Sebastian; Kwiecień, Michał; Smola-Dmochowska, Anna; Domański, Marian; Janeczek, Henryk; Włodarczyk, Jakub; Klim, Magdalena; Rydz, Joanna; Kawalec, Michał; Sobota, Michał

2018-05-01

The semicrystalline poly(L-lactide) (PLLA) belongs to the materials with shape memory effect (SME) and as a bioresorbable and biocompatible polymer it have found many applications in medical and pharmaceutical field. Assessment of the SME impact on the polymer degradation profile plays crucial role in applications such as drug release systems or in regenerative medicine. Herein, the results of in vitro degradation studies of PLLA samples after SME full test cycle are presented. The samples were loaded and deformed in two manners: progressive and non-progressive. The performed experiments illustrate also influence of the material mechanical damages, caused e.g. during incorrect implantation of PLLA product, on hydrolytic degradation profile. Apparently, degradation profiles are significantly different for the material which was not subjected to the deformation and the deformed ones. The materials after deformation of 50% (in SME cycle) was characterized by non-reversible morphology changes. The effect was observed in deformed samples during the SME test which were carried out ten times. Copyright © 2018 Elsevier Ltd. All rights reserved.

Method for loading shape memory polymer gripper mechanisms

DOEpatents

Lee, Abraham P.; Benett, William J.; Schumann, Daniel L.; Krulevitch, Peter A.; Fitch, Joseph P.

2002-01-01

A method and apparatus for loading deposit material, such as an embolic coil, into a shape memory polymer (SMP) gripping/release mechanism. The apparatus enables the application of uniform pressure to secure a grip by the SMP mechanism on the deposit material via differential pressure between, for example, vacuum within the SMP mechanism and hydrostatic water pressure on the exterior of the SMP mechanism. The SMP tubing material of the mechanism is heated to above the glass transformation temperature (Tg) while reshaping, and subsequently cooled to below Tg to freeze the shape. The heating and/or cooling may, for example, be provided by the same water applied for pressurization or the heating can be applied by optical fibers packaged to the SMP mechanism for directing a laser beam, for example, thereunto. At a point of use, the deposit material is released from the SMP mechanism by reheating the SMP material to above the temperature Tg whereby it returns to its initial shape. The reheating of the SMP material may be carried out by injecting heated fluid (water) through an associated catheter or by optical fibers and an associated beam of laser light, for example.

Fabrication of a Bioactive, PCL-based "Self-fitting" Shape Memory Polymer Scaffold.

PubMed

Nail, Lindsay N; Zhang, Dawei; Reinhard, Jessica L; Grunlan, Melissa A

2015-10-23

Tissue engineering has been explored as an alternative strategy for the treatment of critical-sized cranio-maxillofacial (CMF) bone defects. Essential to the success of this approach is a scaffold that is able to conformally fit within an irregular defect while also having the requisite biodegradability, pore interconnectivity and bioactivity. By nature of their shape recovery and fixity properties, shape memory polymer (SMP) scaffolds could achieve defect "self-fitting." In this way, following exposure to warm saline (~60 ºC), the SMP scaffold would become malleable, permitting it to be hand-pressed into an irregular defect. Subsequent cooling (~37 ºC) would return the scaffold to its relatively rigid state within the defect. To meet these requirements, this protocol describes the preparation of SMP scaffolds prepared via the photochemical cure of biodegradable polycaprolactone diacrylate (PCL-DA) using a solvent-casting particulate-leaching (SCPL) method. A fused salt template is utilized to achieve pore interconnectivity. To realize bioactivity, a polydopamine coating is applied to the surface of the scaffold pore walls. Characterization of self-fitting and shape memory behaviors, pore interconnectivity and in vitro bioactivity are also described.

Three-Dimensional Flexible Electronics Enabled by Shape Memory Polymer Substrates for Responsive Neural Interfaces.

PubMed

Ware, Taylor; Simon, Dustin; Hearon, Keith; Liu, Clive; Shah, Sagar; Reeder, Jonathan; Khodaparast, Navid; Kilgard, Michael P; Maitland, Duncan J; Rennaker, Robert L; Voit, Walter E

2012-12-01

Planar electronics processing methods have enabled neural interfaces to become more precise and deliver more information. However, this processing paradigm is inherently 2D and rigid. The resulting mechanical and geometrical mismatch at the biotic-abiotic interface can elicit an immune response that prevents effective stimulation. In this work, a thiol-ene/acrylate shape memory polymer is utilized to create 3D softening substrates for stimulation electrodes. This substrate system is shown to soften in vivo from more than 600 to 6 MPa. A nerve cuff electrode that coils around the vagus nerve in a rat and that drives neural activity is demonstrated.

Programmable, reversible and repeatable wrinkling of shape memory polymer thin films on elastomeric substrates for smart adhesion.

PubMed

Wang, Yu; Xiao, Jianliang

2017-08-09

Programmable, reversible and repeatable wrinkling of shape memory polymer (SMP) thin films on elastomeric polydimethylsiloxane (PDMS) substrates is realized, by utilizing the heat responsive shape memory effect of SMPs. The dependencies of wrinkle wavelength and amplitude on program strain and SMP film thickness are shown to agree with the established nonlinear buckling theory. The wrinkling is reversible, as the wrinkled SMP thin film can be recovered to the flat state by heating up the bilayer system. The programming cycle between wrinkle and flat is repeatable, and different program strains can be used in different programming cycles to induce different surface morphologies. Enabled by the programmable, reversible and repeatable SMP film wrinkling on PDMS, smart, programmable surface adhesion with large tuning range is demonstrated.

Thermorheological characteristics and comparison of shape memory polymers fabricated by novel 3D printing technique

NASA Astrophysics Data System (ADS)

Hassan, Rizwan Ul; Jo, Soohwan; Seok, Jongwon

The feasibility of fabrication of shape memory polymers (SMPs) was investigated using a customized 3-dimensional (3D) printing technique with an excellent resolution that could be less than 100 microns. The thermorheological effects of SMPs were adjusted by contact and non-contact triggering, which led to the respective excellent shape recoveries of 100% and 99.89%. Thermogravimetric analyses of SMPs resulted in a minor weight loss, thereby revealing good thermal stability at higher temperatures. The viscoelastic properties of SMPs were measured using dynamic mechanical analyses, exhibiting increased viscous and elastic characteristics. Mechanical strength, thermal stability and viscoelastic properties, of the two SMPs were compared [di(ethylene) glycol dimethacrylate (DEGDMA) and poly (ethylene glycol) dimethacrylate (PEGDMA)] to investigate the shape memory behavior. This novel 3D printing technique can be used as a promising method for fabricating smart materials with increased accuracy in a cost-effective manner.

Revealing the glass transition in shape memory polymers using Brillouin spectroscopy

NASA Astrophysics Data System (ADS)

Steelman, Zachary A.; Weems, Andrew C.; Traverso, Andrew J.; Szafron, Jason M.; Maitland, Duncan J.; Yakovlev, Vladislav V.

2017-12-01

Emerging medical devices which employ shape memory polymers (SMPs) require precise measurements of the glass transition temperature (Tg) to ensure highly controlled shape recovery kinetics. Conventional techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have limitations that prevent utilization for certain devices, including limited accuracy and the need for sacrificial samples. In this report, we employ an approach based on Brillouin spectroscopy to probe the glass transition of SMPs rapidly, remotely, and nondestructively. Further, we compare the Tg obtained from Brillouin scattering with DMA- and DSC-measured Tg to demonstrate the accuracy of Brillouin scattering for this application. We conclude that Brillouin spectroscopy is an accurate technique for obtaining the glass transition temperature of SMPs, aligning closely with the most common laboratory standards while providing a rapid, remote, and nondestructive method for the analysis of unique polymeric medical devices.

Therapeutic effect of mesenchymal multipotent stromal cells on memory in animals with Alzheimer-type neurodegeneration.

PubMed

Bobkova, N V; Poltavtseva, R A; Samokhin, A N; Sukhikh, G T

2013-11-01

Transplantation of human mesenchymal multipotent stromal cells improved spatial memory in bulbectomized mice with Alzheimer-type neurodegeneration. The positive effect was observed in 1 month after intracerebral transplantation and in 3 months after systemic injection of mesenchymal multipotent stromal cells. No cases of malignant transformation were noted. These findings indicate prospects of using mesenchymal multipotent stromal cells for the therapy of Alzheimer disease and the possibility of their systemic administration for attaining the therapeutic effect.

Drug delivery's quest for polymers: Where are the frontiers?

PubMed

Merkle, Hans P

2015-11-01

Since the legendary 1964 article of Folkman and Long entitled "The use of silicone rubber as a carrier for prolonged drug therapy" the role of polymers in controlled drug delivery has come a long way. Today it is evident that polymers play a crucial if not the prime role in this field. The latest boost owes to the interest in drug delivery for the purpose of tissue engineering in regenerative medicine. The focus of this commentary is on a selection of general and personal observations that are characteristic for the current state of polymer therapeutics and carriers. It briefly highlights selected examples for the long march of synthetic polymer-drug conjugates from bench to bedside, comments on the ambivalence of selected polymers as inert excipients versus biological response modifiers, and on the yet unsolved dilemma of cationic polymers for the delivery of nucleic acid therapeutics. Further subjects are the complex design of multifunctional polymeric carriers including recent concepts towards functional supramolecular polymers, as well as observations on stimuli-sensitive polymers and the currently ongoing trend towards natural and naturally-derived biopolymers. The final topic is the discovery and early development of a novel type of biodegradable polyesters for parenteral use. Altogether, it is not the basic and applied research in polymer therapeutics and carriers, but the translational process that is the key hurdle to proceed towards an authoritative approval of new polymer therapeutics and carriers. Copyright © 2015 Elsevier B.V. All rights reserved.

A stress-induced phase transition model for semi-crystallize shape memory polymer

NASA Astrophysics Data System (ADS)

Guo, Xiaogang; Zhou, Bo; Liu, Liwu; Liu, Yanju; Leng, Jinsong

2014-03-01

The developments of constitutive models for shape memory polymer (SMP) have been motivated by its increasing applications. During cooling or heating process, the phase transition which is a continuous time-dependent process happens in semi-crystallize SMP and the various individual phases form at different temperature and in different configuration. Then, the transformation between these phases occurred and shape memory effect will emerge. In addition, stress applied on SMP is an important factor for crystal melting during phase transition. In this theory, an ideal phase transition model considering stress or pre-strain is the key to describe the behaviors of shape memory effect. So a normal distributed model was established in this research to characterize the volume fraction of each phase in SMP during phase transition. Generally, the experiment results are partly backward (in heating process) or forward (in cooling process) compared with the ideal situation considering delay effect during phase transition. So, a correction on the normal distributed model is needed. Furthermore, a nonlinear relationship between stress and phase transition temperature Tg is also taken into account for establishing an accurately normal distributed phase transition model. Finally, the constitutive model which taking the stress as an influence factor on phase transition was also established. Compared with the other expressions, this new-type model possesses less parameter and is more accurate. For the sake of verifying the rationality and accuracy of new phase transition and constitutive model, the comparisons between the simulated and experimental results were carried out.

Resistive Switching Memory Phenomena in PEDOT PSS: Coexistence of Switchable Diode Effect and Write Once Read Many Memory

PubMed Central

Nguyen, Viet Cuong; Lee, Pooi See

2016-01-01

We study resistive switching memory phenomena in conducting polymer PEDOT PSS. In the same film, there are two types of memory behavior coexisting; namely, the switchable diode effect and write once read many memory. This is the first report on switchable diode phenomenon based on conducting organic materials. The effect was explained as charge trapping of PEDOT PSS film and movement of proton. The same PEDOT PSS device also exhibits write once read many memory (WORM) phenomenon which arises due to redox reaction that reduces PEDOT PSS and renders it non-conducting. The revelation of these two types of memory phenomena in PEDOT PSS highlights the remarkable versatility of this conducting conjugated polymer. PMID:26806868

Modeling the Coupled Chemo-Thermo-Mechanical Behavior of Amorphous Polymer Networks.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zimmerman, Jonathan A.; Nguyen, Thao D.; Xiao, Rui

2015-02-01

Amorphous polymers exhibit a rich landscape of time-dependent behavior including viscoelasticity, structural relaxation, and viscoplasticity. These time-dependent mechanisms can be exploited to achieve shape-memory behavior, which allows the material to store a programmed deformed shape indefinitely and to recover entirely the undeformed shape in response to specific environmental stimulus. The shape-memory performance of amorphous polymers depends on the coordination of multiple physical mechanisms, and considerable opportunities exist to tailor the polymer structure and shape-memory programming procedure to achieve the desired performance. The goal of this project was to use a combination of theoretical, numerical and experimental methods to investigate themore » effect of shape memory programming, thermo-mechanical properties, and physical and environmental aging on the shape memory performance. Physical and environmental aging occurs during storage and through exposure to solvents, such as water, and can significantly alter the viscoelastic behavior and shape memory behavior of amorphous polymers. This project – executed primarily by Professor Thao Nguyen and Graduate Student Rui Xiao at Johns Hopkins University in support of a DOE/NNSA Presidential Early Career Award in Science and Engineering (PECASE) – developed a theoretical framework for chemothermo- mechanical behavior of amorphous polymers to model the effects of physical aging and solvent-induced environmental factors on their thermoviscoelastic behavior.« less

Laser-Activated Shape Memory Polymer Microactuator for Thrombus Removal Following Ischemic Stroke: Preliminary In Vitro Analysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small, W; Metzger, M F; Wilson, T S

2004-09-23

Due to the narrow (3-hour) treatment window for effective use of the thrombolytic drug recombinant tissue-type plasminogen activator (rt-PA), there is a need to develop alternative treatments for ischemic stroke. We are developing an intravascular device for mechanical thrombus removal using shape memory polymer (SMP). We propose to deliver the SMP microactuator in its secondary straight rod form (length = 4 cm, diameter = 350 {micro}m) through a catheter distal to the vascular occlusion. The microactuator, which is mounted on the end of an optical fiber, is then transformed into its primary corkscrew shape by laser heating (diode laser, {lambda}more » = 800 nm) above its soft phase glass transition temperature (T{sub gs} = 55 C). Once deployed, the microactuator is retracted and the captured thrombus is removed to restore blood flow. The SMP is doped with indocyanine green (ICG) dye to increase absorption of the laser light. Successful deployment of the microactuator depends on the optical properties of the ICG-doped SMP and the optical coupling efficiency of the interface between the optical fiber and the SMP. Spectrophotometry, thermal imaging, and computer simulation aided the initial design effort and continue to be useful tools for optimization of the dye concentration and laser power. Thermomechanical testing was performed to characterize the elastic modulus of the SMP. We have demonstrated laser-activation of the SMP microactuator in air at room temperature, suggesting this concept is a promising therapeutic alternative to rt-PA.« less

Integrin-assisted drug delivery of nano-scaled polymer therapeutics bearing paclitaxel.

PubMed

Eldar-Boock, Anat; Miller, Keren; Sanchis, Joaquin; Lupu, Ruth; Vicent, María J; Satchi-Fainaro, Ronit

2011-05-01

Angiogenesis plays a prominent role in cancer progression. Anti-angiogenic therapy therefore, either alone or in combination with conventional cytotoxic therapy, offers a promising therapeutic approach. Paclitaxel (PTX) is a widely-used potent cytotoxic drug that also exhibits anti-angiogenic effects at low doses. However, its use, at its full potential, is limited by severe side effects. Here we designed and synthesized a targeted conjugate of PTX, a polymer and an integrin-targeted moiety resulting in a polyglutamic acid (PGA)-PTX-E-[c(RGDfK)(2)] nano-scaled conjugate. Polymer conjugation converted PTX to a macromolecule, which passively targets the tumor tissue exploiting the enhanced permeability and retention effect, while extravasating via the leaky tumor neovasculature. The cyclic RGD peptidomimetic enhanced the effects previously seen for PGA-PTX alone, utilizing the additional active targeting to the α(v)β(3) integrin overexpressed on tumor endothelial and epithelial cells. This strategy is particularly valuable when tumors are well-vascularized, but they present poor vascular permeability. We show that PGA is enzymatically-degradable leading to PTX release under lysosomal acidic pH. PGA-PTX-E-[c(RGDfK)(2)] inhibited the growth of proliferating α(v)β(3)-expressing endothelial cells and several cancer cells. We also showed that PGA-PTX-E-[c(RGDfK)(2)] blocked endothelial cells migration towards vascular endothelial growth factor; blocked capillary-like tube formation; and inhibited endothelial cells attachment to fibrinogen. Orthotopic studies in mice demonstrated preferential tumor accumulation of the RGD-bearing conjugate, leading to enhanced anti-tumor efficacy and a marked decrease in toxicity as compared with free PTX-treated mice. Copyright © 2011 Elsevier Ltd. All rights reserved.

Polymer Nanoparticles as Smart Carriers for the Enhanced Release of Therapeutic Agents to the CNS.

PubMed

Gagliardi, Mariacristina; Borri, Claudia

2017-01-01

The brain is the most protected organ in the human body; its protective shield, relying on a complex system of cells, proteins and transporters, prevents potentially harmful substances from entering the brain from the bloodstream but, on the other hand, it also stops drugs administered via the systemic route. To improve the efficacy of pharmacological treatments, targeted drug delivery by means of polymer nanoparticles is a challenging but, at the same time, efficient strategy. Thanks to a highly multidisciplinary approach, several ways to overcome the brain protection have provided effective solutions to treat a large number of diseases. Important advances in polymer science, together with the development of novel techniques for nanocarrier preparation, and the discovery of novel targeting ligands and molecules, allow a fine-tuning of size, shape, chemicophysical properties and surface chemistry of functional particulate systems; it enables the improvement of the therapeutic performances for several drugs, also toward districts that are difficult to be treated, such as the brain. This review focuses on the great strides made from scientists and doctors in the development of polymer nano-sized drug delivery systems for brain diseases. Even though the optimal nanocarrier was not yet discovered, important advances were made to strive for safer, performant and successful systems, with the expectation to find soon better solutions to cure some still untreatable pathologies. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Drug-conjugated polymers as gene carriers for synergistic therapeutic effect.

PubMed

Pofali, P A; Singh, B; Dandekar, P; Jain, R D; Maharjan, S; Choi, Y J; Arote, R B; Cho, C S

2016-05-01

The ability to safely and effectively transfer gene into cells is the fundamental goal of gene delivery. In spite of the best efforts of researchers around the world, gene therapy has limited success. This may be because of several limitations of delivering gene which is one of the greatest technical challenges in the modern medicine. To address these issues, many efforts have been made to bind drugs and genes together by polymers for co-delivery to achieve synergistic effect. Usually, binding interaction of drugs with polymers is either physical or chemical. In case of drug-polymer physical interaction, the efficiency of drugs generally decreases because of separation of drugs from polymers in vivo whenever it comes in contact with charged biofluid/s or cells. While chemical interaction of drug-polymer overcomes the aforementioned obstacle, several problems such as steric hindrance, solubility, and biodegradability hinder it to develop as gene carrier. Considering these benefits and pitfalls, the objective of this review is to discuss the possible extent of drug-conjugated polymers as safe and efficient gene delivery carriers for achieving synergistic effect to combat various genetic disorders. © 2015 Wiley Periodicals, Inc.

Self-Deploying Trusses Containing Shape-Memory Polymers

NASA Technical Reports Server (NTRS)

Schueler, Robert M.

2008-01-01

Composite truss structures are being developed that can be compacted for stowage and later deploy themselves to full size and shape. In the target applications, these smart structures will precisely self-deploy and support a large, lightweight space-based antenna. Self-deploying trusses offer a simple, light, and affordable alternative to articulated mechanisms or inflatable structures. The trusses may also be useful in such terrestrial applications as variable-geometry aircraft components or shelters that can be compacted, transported, and deployed quickly in hostile environments. The truss technology uses high-performance shape-memory-polymer (SMP) thermoset resin reinforced with fibers to form a helical composite structure. At normal operating temperatures, the truss material has the structural properties of a conventional composite. This enables truss designs with required torsion, bending, and compression stiffness. However, when heated to its designed glass transition temperature (Tg), the SMP matrix acquires the flexibility of an elastomer. In this state, the truss can be compressed telescopically to a configuration encompassing a fraction of its original volume. When cooled below Tg, the SMP reverts to a rigid state and holds the truss in the stowed configuration without external constraint. Heating the materials above Tg activates truss deployment as the composite material releases strain energy, driving the truss to its original memorized configuration without the need for further actuation. Laboratory prototype trusses have demonstrated repeatable self-deployment cycles following linear compaction exceeding an 11:1 ratio (see figure).

A low switching voltage organic-on-inorganic heterojunction memory element utilizing a conductive polymer fuse on a doped silicon substrate

NASA Astrophysics Data System (ADS)

Smith, Shawn; Forrest, Stephen R.

2004-06-01

We present a simple, nonvolatile, write-once-read-many-times (WORM) memory device utilizing an organic-on-inorganic heterojunction (OI-HJ) diode with a conductive polymer fuse consisting of polyethylene dioxythiophene:polysterene sulfonic acid (PEDOT:PSS) forming one side of the rectifying junction. Current transients are used to change the fuse from a conducting to a nonconducting state to record a logical "1" or "0", while the nonlinearity of the OI-HJ allows for passive matrix memory addressing. The device switches at 2 and 4 V for 50 nm thick PEDOT:PSS films on p-type Si and n-type Si, respectively. This is significantly lower than the switching voltage used in PEDOT:PSS/p-i-n Si memory elements [J. Appl Phys. 94, 7811 (2003)]. The switching results in a permanent reduction of forward-bias current by approximately five orders of magnitude. These results suggest that the OI-HJ structure has potential for use in low-cost passive matrix WORM memories for archival storage applications.

Shape memory polymer foams for endovascular therapies

DOEpatents

Wilson, Thomas S.; Maitland, Duncan J.

2017-03-21

A system for occluding a physical anomaly. One embodiment comprises a shape memory material body wherein the shape memory material body fits within the physical anomaly occluding the physical anomaly. The shape memory material body has a primary shape for occluding the physical anomaly and a secondary shape for being positioned in the physical anomaly.

Shape memory polymer foams for endovascular therapies

DOEpatents

Wilson, Thomas S [Castro Valley, CA; Maitland, Duncan J [Pleasant Hill, CA

2012-03-13

A system for occluding a physical anomaly. One embodiment comprises a shape memory material body wherein the shape memory material body fits within the physical anomaly occluding the physical anomaly. The shape memory material body has a primary shape for occluding the physical anomaly and a secondary shape for being positioned in the physical anomaly.

Shape memory polymer foams for endovascular therapies

DOEpatents

Wilson, Thomas S.; Maitland, Duncan J.

2015-05-26

A system for occluding a physical anomaly. One embodiment comprises a shape memory material body wherein the shape memory material body fits within the physical anomaly occluding the physical anomaly. The shape memory material body has a primary shape for occluding the physical anomaly and a secondary shape for being positioned in the physical anomaly.

Dually actuated triple shape memory polymers of cross-linked polycyclooctene-carbon nanotube/polyethylene nanocomposites.

PubMed

Wang, Zhenwen; Zhao, Jun; Chen, Min; Yang, Minhao; Tang, Luyang; Dang, Zhi-Min; Chen, Fenghua; Huang, Miaoming; Dong, Xia

2014-11-26

In this work, electrically and thermally actuated triple shape memory polymers (SMPs) of chemically cross-linked polycyclooctene (PCO)-multiwalled carbon nanotube (MWCNT)/polyethylene (PE) nanocomposites with co-continuous structure and selective distribution of fillers in PCO phase are prepared. We systematically studied not only the microstructure including morphology and fillers' selective distribution in one phase of the PCO/PE blends, but also the macroscopic properties including thermal, mechanical, and electrical properties. The co-continuous window of the immiscible PCO/PE blends is found to be the volume fraction of PCO (vPCO) of ca. 40-70 vol %. The selective distribution of fillers in one phase of co-continuous blends is obtained by a masterbatch technique. The prepared triple SMP materials show pronounced triple shape memory effects (SMEs) on the dynamic mechanical thermal analysis (DMTA) and the visual observation by both thermal and electric actuations. Such polyolefin samples with well-defined microstructure, electrical actuation, and triple SMEs might have potential applications as, for example, multiple autochoke elements for engines, self-adjusting orthodontic wires, and ophthalmic devices.

Revealing the glass transition in shape memory polymers using Brillouin spectroscopy.

PubMed

Steelman, Zachary A; Weems, Andrew C; Traverso, Andrew J; Szafron, Jason M; Maitland, Duncan J; Yakovlev, Vladislav V

2017-12-11

Emerging medical devices which employ shape memory polymers (SMPs) require precise measurements of the glass transition temperature (T g ) to ensure highly controlled shape recovery kinetics. Conventional techniques like differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) have limitations that prevent utilization for certain devices, including limited accuracy and the need for sacrificial samples. In this report, we employ an approach based on Brillouin spectroscopy to probe the glass transition of SMPs rapidly, remotely, and nondestructively. Further, we compare the T g obtained from Brillouin scattering with DMA- and DSC-measured T g to demonstrate the accuracy of Brillouin scattering for this application. We conclude that Brillouin spectroscopy is an accurate technique for obtaining the glass transition temperature of SMPs, aligning closely with the most common laboratory standards while providing a rapid, remote, and nondestructive method for the analysis of unique polymeric medical devices.

Therapeutic-Ultrasound-Triggered Shape Memory of a Melamine-Enhanced Poly(vinyl alcohol) Physical Hydrogel.

PubMed

Li, Guo; Yan, Qiang; Xia, Hesheng; Zhao, Yue

2015-06-10

Therapeutic-ultrasound-triggered shape memory was demonstrated for the first time with a melamine-enhanced poly(vinyl alcohol) (PVA) physical hydrogel. The addition of a small amount of melamine (up to 1.5 wt %) in PVA results in a strong hydrogel due to the multiple H-bonding between the two constituents. A temporary shape of the hydrogel can be obtained by deformation of the hydrogel (∼65 wt % water) at room temperature, followed by fixation of the deformation by freezing/thawing the hydrogel under strain, which induces crystallization of PVA. We show that the ultrasound delivered by a commercially available device designed for the patient's pain relief could trigger the shape recovery process as a result of ultrasound-induced local heating in the hydrogel that melts the crystallized PVA cross-linking. This hydrogel is thus interesting for potential applications because it combines many desirable properties, being mechanically strong, biocompatible, and self-healable and displaying the shape memory capability triggered by a physiological stimulus.

Inorganic-organic shape memory polymers and foams for bone defect repairs

NASA Astrophysics Data System (ADS)

Zhang, Dawei

The ultimate goal of this research was to develop a "self-fitting" shape memory polymer (SMP) scaffold for the repair of craniomaxillofacial (CMF) bone defects. CMF defects may be caused by trauma, tumor removal or congenital abnormalities and represent a major class of bone defects. Their repair with autografts is limited by availability, donor site morbidity and complex surgical procedures. In addition, shaping and positioning of these rigid grafts into irregular defects is difficult. Herein, we have developed SMP scaffolds which soften at T > ˜56 °C, allowing them to conformally fit into a bone defect. Upon cooling to body temperature, the scaffold becomes rigid and mechanically locks in place. This research was comprised of four major studies. In the first study, photocrosslinkable acrylated (AcO) SMP macromers containing a poly(epsilon-caprolactone) (PCL) segment and polydimethylsiloxane (PDMS) segments were synthesized with the general formula: AcO-PCL40-block-PDMS m-block-PCL40-OAc. By varying the PDMS segment length (m), solid SMPs with highly tunable mechanical properties and excellent shape memory abilities were prepared. In the second study, porous SMP scaffolds were fabricated based on AcO-PCL 40-block-PDMS37-block-PCL 40-OAc via a revised solvent casting particulate leaching (SCPL) method. By tailoring scaffold parameters including salt fusion, macromer concentration and salt size, scaffold properties (e.g. pore features, compressive modulus and shape memory behavior) were tuned. In the third study, porous SMP scaffolds were produced from macromers with variable PDMS segment lengths (m = 0 -- 130) via an optimized SCPL method. The impact on pore features, thermal, mechanical, and shape memory properties as well as degradation rates were investigated. In the final study, a bioactive polydopamine coating was applied onto pore surfaces of the SMP scaffold prepared from PCL diacrylate. The thin coating did not affect intrinsic bulk properties of the

Reticulation of low density shape memory polymer foam with an in vivo demonstration of vascular occlusion

PubMed Central

Rodriguez, Jennifer N.; Miller, Matthew W.; Boyle, Anthony; Horn, John; Yang, Cheng-Kang; Wilson, Thomas S.; Ortega, Jason M.; Small, Ward; Nash, Landon; Skoog, Hunter; Maitland, Duncan J.

2014-01-01

Predominantly closed-cell low density shape memory polymer (SMP) foam was recently reported to be an effective aneurysm filling device in a porcine model (Rodriguez et al., Journal of Biomedical Materials Research Part A 2013: (http://dx.doi.org/10.1002/jbm.a.34782)). Because healing involves blood clotting and cell migration throughout the foam volume, a more open-cell structure may further enhance the healing response. This research sought to develop a non-destructive reticulation process for this SMP foam to disrupt the membranes between pore cells. Non-destructive mechanical reticulation was achieved using a gravity-driven floating nitinol pin array coupled with vibratory agitation of the foam and supplemental chemical etching. Reticulation resulted in a reduced elastic modulus and increased permeability, but did not impede shape memory behavior. Reticulated foams were capable of achieving rapid vascular occlusion in an in vivo porcine model. PMID:25222869

Polymer donors of nitric oxide improve the treatment of experimental solid tumours with nanosized polymer therapeutics.

PubMed

Šírová, Milada; Horková, Veronika; Etrych, Tomáš; Chytil, Petr; Říhová, Blanka; Studenovský, Martin

Polymer carriers based on N-(2-hydroxypropyl)methacrylamide (HPMA) copolymers with incorporated organic nitrates as nitric oxide (NO) donors were designed with the aim to localise NO generation in solid tumours, thus highly increasing the enhanced permeability and retention (EPR) effect. The NO donors were coupled to the polymer carrier either through a stable bond or through a hydrolytically degradable, pH sensitive, bond. In vivo, the co-administration of the polymer NO donor and HPMA copolymer-bound cytotoxic drug (doxorubicin; Dox) resulted in an improvement in the treatment of murine EL4 T-cell lymphoma. The polymer NO donors neither potentiated the in vitro toxicity of the cytotoxic drug nor exerted any effect on in vivo model without the EPR effect, such as BCL1 leukaemia. Thus, an increase in passive accumulation of the nanomedicine carrying cytotoxic drug via NO-enhanced EPR effect was the operative mechanism of action. The most significant improvement in the therapy was observed in a combination treatment with such a polymer conjugate of Dox, which is characterised by increased circulation in the blood and efficient accumulation in solid tumours. Notably, the combination treatment enabled the development of an anti-tumour immune response, which was previously demonstrated as an important feature of HPMA-based polymer cytotoxic drugs.

ERP evidence of preserved early memory function in term infants with neonatal encephalopathy following therapeutic hypothermia.

PubMed

Pfister, Katie M; Zhang, Lei; Miller, Neely C; Hultgren, Solveig; Boys, Chris J; Georgieff, Michael K

2016-12-01

Neonatal encephalopathy (NE) carries high risk for neurodevelopmental impairments. Therapeutic hypothermia (TH) reduces this risk, particularly for moderate encephalopathy (ME). Nevertheless, these infants often have subtle functional deficits, including abnormal memory function. Detection of deficits at the earliest possible time-point would allow for intervention during a period of maximal brain plasticity. Recognition memory function in 22 infants with NE treated with TH was compared to 23 healthy controls using event-related potentials (ERPs) at 2 wk of age. ERPs were recorded to mother's voice alternating with a stranger's voice to assess attentional responses (P2), novelty detection (slow wave), and discrimination between familiar and novel (difference wave). Development was tested at 12 mo using the Bayley Scales of Infant Development, Third Edition (BSID-III). The NE group showed similar ERP components and BSID-III scores to controls. However, infants with NE showed discrimination at midline leads (P = 0.01), whereas controls showed discrimination in the left hemisphere (P = 0.05). Normal MRI (P = 0.05) and seizure-free electroencephalogram (EEG) (P = 0.04) correlated positively with outcomes. Infants with NE have preserved recognition memory function after TH. The spatially different recognition memory processing after early brain injury may represent compensatory changes in the brain circuitry and reflect a benefit of TH.

A phenomenological model for simulating the chemo-responsive shape memory effect in polymers undergoing a permeation transition

NASA Astrophysics Data System (ADS)

Lu, Haibao; Huang, Wei Min; Leng, Jinsong

2014-04-01

We present a phenomenological model for studying the constitutive relations and working mechanism of the chemo-responsive shape memory effect (SME) in shape memory polymers (SMPs). On the basis of the solubility parameter equation, diffusion model and permeation transition model, a phenomenological model is derived for quantitatively identifying the influential factors in the chemically induced SME in SMPs. After this, a permeability parallel model and series model are implemented in order to couple the constitutive relations of the permeability coefficient, stress and relaxation time as a function of stretch, separately. The inductive effect of the permeability transition on the transition temperature is confirmed as the driving force for the chemo-responsive SME. Furthermore, the analytical result from the phenomenological model is compared with the available experimental results and the simulation of a semi-empirical model reported in the literature for verification.

Silicone Membranes to Inhibit Water Uptake into Thermoset Polyurethane Shape-Memory Polymer Conductive Composites

PubMed Central

Yu, Ya-Jen; Infanger, Stephen; Grunlan, Melissa A.; Maitland, Duncan J.

2014-01-01

Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature (Tg) resulting in shape recovery in vivo. While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo. In this study, a silicone membrane was used to inhibit water uptake into a thermoset SMP composite containing conductive filler. Thermoset polyurethane (PU) SMPs were loaded with either 5 wt% carbon black (CB) or 5 wt% carbon nanotubes (CNT) and subsequently coated with either an Al2O3- or silica-filled silicone membrane. It was observed that the silicone membranes, particularly the silica-filled membrane, reduced the rate of water absorption (37 °C) and subsequent Tg depression versus uncoated composites. In turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37 °C. PMID:25663711

Silicone Membranes to Inhibit Water Uptake into Thermoset Polyurethane Shape-Memory Polymer Conductive Composites.

PubMed

Yu, Ya-Jen; Infanger, Stephen; Grunlan, Melissa A; Maitland, Duncan J

2015-01-05

Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature ( T g ) resulting in shape recovery in vivo . While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo . In this study, a silicone membrane was used to inhibit water uptake into a thermoset SMP composite containing conductive filler. Thermoset polyurethane (PU) SMPs were loaded with either 5 wt% carbon black (CB) or 5 wt% carbon nanotubes (CNT) and subsequently coated with either an Al 2 O 3 - or silica-filled silicone membrane. It was observed that the silicone membranes, particularly the silica-filled membrane, reduced the rate of water absorption (37 °C) and subsequent T g depression versus uncoated composites. In turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37 °C.

Shape Recovery with Concomitant Mechanical Strengthening of Amphiphilic Shape Memory Polymers in Warm Water

DOE PAGES

Zhang, Ben; DeBartolo, Janae E.; Song, Jie

2017-01-26

Maintaining adequate or enhancing mechanical properties of shape memory polymers (SMPs) after shape recovery in an aqueous environment are greatly desired for biomedical applications of SMPs as self-fitting tissue scaffolds or minimally invasive surgical implants. Here we report stable temporary shape fixing and facile shape recovery of biodegradable triblock amphiphilic SMPs containing a poly(ethylene glycol) (PEG) center block and flanking poly(lactic acid) or poly(lactic-co-glycolic acid) blocks in warm water, accompanied with concomitant enhanced mechanical strengths. Differential scanning calorimetry (DSC), wide-angle X-ray diffraction (WXRD) and small-angle X-ray scattering (SAXS) analyses revealed that the unique stiffening of the amphiphilic SMPs upon hydrationmore » was due to hydration-driven microphase separation and PEG crystallization. We further demonstrated that the chemical composition of degradable blocks in these SMPs could be tailored to affect the persistence of hydration-induced stiffening upon subsequent dehydration. These properties combined open new horizons for these amphiphilic SMPs for smart weight-bearing in vivo applications (e.g. as self-fitting intervertebral discs). In conclusion, this study also provides a new material design strategy to strengthen polymers in aqueous environment in general.« less

Silicone membranes to inhibit water uptake into thermoset polyurethane shape-memory polymer conductive composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Ya-Jen; Infanger, Stephen; Grunlan, Melissa A.

Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature (T g) resulting in shape recovery in vivo. While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo. In this paper, a silicone membrane was used to inhibit water uptake into a thermoset SMPmore » composite containing conductive filler. Thermoset polyurethane SMPs were loaded with either 5 wt % carbon black or 5 wt % carbon nanotubes, and subsequently coated with either an Al 2O 3- or silica-filled silicone membrane. It was observed that the silicone membranes, particularly the silica-filled membrane, reduced the rate of water absorption (37°C) and subsequent T g depression versus uncoated composites. Finally, in turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37°C.« less

Silicone membranes to inhibit water uptake into thermoset polyurethane shape-memory polymer conductive composites

DOE PAGES

Yu, Ya-Jen; Infanger, Stephen; Grunlan, Melissa A.; ...

2014-07-24

Electroactive shape memory polymer (SMP) composites capable of shape actuation via resistive heating are of interest for various biomedical applications. However, water uptake into SMPs will produce a depression of the glass transition temperature (T g) resulting in shape recovery in vivo. While water actuated shape recovery may be useful, it is foreseen to be undesirable during early periods of surgical placement into the body. Silicone membranes have been previously reported to prevent release of conductive filler from an electroactive polymer composite in vivo. In this paper, a silicone membrane was used to inhibit water uptake into a thermoset SMPmore » composite containing conductive filler. Thermoset polyurethane SMPs were loaded with either 5 wt % carbon black or 5 wt % carbon nanotubes, and subsequently coated with either an Al 2O 3- or silica-filled silicone membrane. It was observed that the silicone membranes, particularly the silica-filled membrane, reduced the rate of water absorption (37°C) and subsequent T g depression versus uncoated composites. Finally, in turn, this led to a reduction in the rate of recovery of the permanent shape when exposed to water at 37°C.« less

Potential Therapeutic Effects of Lipoic Acid on Memory Deficits Related to Aging and Neurodegeneration.

PubMed

Molz, Patrícia; Schröder, Nadja

2017-01-01

The aging process comprises a series of organic alterations, affecting multiple systems, including the nervous system. Aging has been considered the main risk factor for the advance of neurodegenerative diseases, many of which are accompanied by cognitive impairment. Aged individuals show cognitive decline, which has been associated with oxidative stress, as well as mitochondrial, and consequently energetic failure. Lipoic acid (LA), a natural compound present in food and used as a dietary supplement, has been considered a promising agent for the treatment and/or prevention of neurodegenerative disorders. In spite of a number of preclinical studies showing beneficial effects of LA in memory functioning, and pointing to its neuroprotective potential effect, to date only a few studies have examined its effects in humans. Investigations performed in animal models of memory loss associated to aging and neurodegenerative disorders have shown that LA improves memory in a variety of behavioral paradigms. Moreover, cell and molecular mechanisms underlying LA effects have also been investigated. Accordingly, LA displays antioxidant, antiapoptotic, and anti-inflammatory properties in both in vivo and in vitro studies. In addition, it has been shown that LA reverses age-associated loss of neurotransmitters and their receptors, which can underlie its effects on cognitive functions. The present review article aimed at summarizing and discussing the main studies investigating the effects of LA on cognition as well as its cell and molecular effects, in order to improve the understanding of the therapeutic potential of LA on memory loss during aging and in patients suffering from neurodegenerative disorders, supporting the development of clinical trials with LA.

Soluble porphyrin polymers

DOEpatents

Gust, Jr., John Devens; Liddell, Paul Anthony

2015-07-07

Porphyrin polymers of Structure 1, where n is an integer (e.g., 1, 2, 3, 4, 5, or greater) ##STR00001## are synthesized by the method shown in FIGS. 2A and 2B. The porphyrin polymers of Structure 1 are soluble in organic solvents such as 2-MeTHF and the like, and can be synthesized in bulk (i.e., in processes other than electropolymerization). These porphyrin polymers have long excited state lifetimes, making the material suitable as an organic semiconductor for organic electronic devices including transistors and memories, as well as solar cells, sensors, light-emitting devices, and other opto-electronic devices.

Shape-Memory Hydrogels: Evolution of Structural Principles To Enable Shape Switching of Hydrophilic Polymer Networks.

PubMed

Löwenberg, Candy; Balk, Maria; Wischke, Christian; Behl, Marc; Lendlein, Andreas

2017-04-18

The ability of hydrophilic chain segments in polymer networks to strongly interact with water allows the volumetric expansion of the material and formation of a hydrogel. When polymer chain segments undergo reversible hydration depending on environmental conditions, smart hydrogels can be realized, which are able to shrink/swell and thus alter their volume on demand. In contrast, implementing the capacity of hydrogels to switch their shape rather than volume demands more sophisticated chemical approaches and structural concepts. In this Account, the principles of hydrogel network design, incorporation of molecular switches, and hydrogel microstructures are summarized that enable a spatially directed actuation of hydrogels by a shape-memory effect (SME) without major volume alteration. The SME involves an elastic deformation (programming) of samples, which are temporarily fixed by reversible covalent or physical cross-links resulting in a temporary shape. The material can reverse to the original shape when these molecular switches are affected by application of a suitable stimulus. Hydrophobic shape-memory polymers (SMPs), which are established with complex functions including multiple or reversible shape-switching, may provide inspiration for the molecular architecture of shape-memory hydrogels (SMHs), but cannot be identically copied in the world of hydrophilic soft materials. For instance, fixation of the temporary shape requires cross-links to be formed also in an aqueous environment, which may not be realized, for example, by crystalline domains from the hydrophilic main chains as these may dissolve in presence of water. Accordingly, dual-shape hydrogels have evolved, where, for example, hydrophobic crystallizable side chains have been linked into hydrophilic polymer networks to act as temperature-sensitive temporary cross-links. By incorporating a second type of such side chains, triple-shape hydrogels can be realized. Considering the typically given light

Reticulation of low density shape memory polymer foam with an in vivo demonstration of vascular occlusion

DOE PAGES

Rodriguez, Jennifer N.; Miller, Matthew W.; Boyle, Anthony; ...

2014-08-11

Recently, predominantly closed-cell low density shape memory polymer (SMP) foam was reported to be an effective aneurysm filling device in a porcine model (Rodriguez et al., Journal of Biomedical Materials Research Part A 2013: (http://dx.doi.org/10.1002/jbm.a.34782)). Because healing involves blood clotting and cell migration throughout the foam volume, a more open-cell structure may further enhance the healing response. This research sought to develop a non-destructive reticulation process for this SMP foam to disrupt the membranes between pore cells. Non-destructive mechanical reticulation was achieved using a gravity-driven floating nitinol pin array coupled with vibratory agitation of the foam and supplemental chemical etching.more » Lastly, reticulation resulted in a reduced elastic modulus and increased permeability, but did not impede the shape memory behavior. Reticulated foams were capable of achieving rapid vascular occlusion in an in vivo porcine model.« less

Multi-shape active composites by 3D printing of digital shape memory polymers

NASA Astrophysics Data System (ADS)

Wu, Jiangtao; Yuan, Chao; Ding, Zhen; Isakov, Michael; Mao, Yiqi; Wang, Tiejun; Dunn, Martin L.; Qi, H. Jerry

2016-04-01

Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers - digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications.

Multi-shape active composites by 3D printing of digital shape memory polymers.

PubMed

Wu, Jiangtao; Yuan, Chao; Ding, Zhen; Isakov, Michael; Mao, Yiqi; Wang, Tiejun; Dunn, Martin L; Qi, H Jerry

2016-04-13

Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers - digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications.

Multi-shape active composites by 3D printing of digital shape memory polymers

PubMed Central

Wu, Jiangtao; Yuan, Chao; Ding, Zhen; Isakov, Michael; Mao, Yiqi; Wang, Tiejun; Dunn, Martin L.; Qi, H. Jerry

2016-01-01

Recent research using 3D printing to create active structures has added an exciting new dimension to 3D printing technology. After being printed, these active, often composite, materials can change their shape over time; this has been termed as 4D printing. In this paper, we demonstrate the design and manufacture of active composites that can take multiple shapes, depending on the environmental temperature. This is achieved by 3D printing layered composite structures with multiple families of shape memory polymer (SMP) fibers – digital SMPs - with different glass transition temperatures (Tg) to control the transformation of the structure. After a simple single-step thermomechanical programming process, the fiber families can be sequentially activated to bend when the temperature is increased. By tuning the volume fraction of the fibers, bending deformation can be controlled. We develop a theoretical model to predict the deformation behavior for better understanding the phenomena and aiding the design. We also design and print several flat 2D structures that can be programmed to fold and open themselves when subjected to heat. With the advantages of an easy fabrication process and the controllable multi-shape memory effect, the printed SMP composites have a great potential in 4D printing applications. PMID:27071543

Temperature dependent evolution of wrinkled single-crystal silicon ribbons on shape memory polymers.

PubMed

Wang, Yu; Yu, Kai; Qi, H Jerry; Xiao, Jianliang

2017-10-25

Shape memory polymers (SMPs) can remember two or more distinct shapes, and thus can have a lot of potential applications. This paper presents combined experimental and theoretical studies on the wrinkling of single-crystal Si ribbons on SMPs and the temperature dependent evolution. Using the shape memory effect of heat responsive SMPs, this study provides a method to build wavy forms of single-crystal silicon thin films on top of SMP substrates. Silicon ribbons obtained from a Si-on-insulator (SOI) wafer are released and transferred onto the surface of programmed SMPs. Then such bilayer systems are recovered at different temperatures, yielding well-defined, wavy profiles of Si ribbons. The wavy profiles are shown to evolve with time, and the evolution behavior strongly depends on the recovery temperature. At relatively low recovery temperatures, both wrinkle wavelength and amplitude increase with time as evolution progresses. Finite element analysis (FEA) accounting for the thermomechanical behavior of SMPs is conducted to study the wrinkling of Si ribbons on SMPs, which shows good agreement with experiment. Merging of wrinkles is observed in FEA, which could explain the increase of wrinkle wavelength observed in the experiment. This study can have important implications for smart stretchable electronics, wrinkling mechanics, stimuli-responsive surface engineering, and advanced manufacturing.

Deformation rate-, hold time-, and cycle-dependent shape-memory performance of Veriflex-E resin

NASA Astrophysics Data System (ADS)

McClung, Amber J. W.; Tandon, Gyaneshwar P.; Baur, Jeffery W.

2013-02-01

Shape-memory polymers have attracted great interest in recent years for application in reconfigurable structures (for instance morphing aircraft, micro air vehicles, and deployable space structures). However, before such applications can be attempted, the mechanical behavior of the shape-memory polymers must be thoroughly understood. The present study represents an assessment of viscous effects during multiple shape-memory cycles of Veriflex-E, an epoxy-based, thermally triggered shape-memory polymer resin. The experimental program is designed to explore the influence of multiple thermomechanical cycles on the shape-memory performance of Veriflex-E. The effects of the deformation rate and hold times at elevated temperature on the shape-memory behavior are also investigated.

Detection of Memory B Activity Against a Therapeutic Protein in Treatment-Naïve Subjects.

PubMed

Liao, Karen; Derbyshire, Stacy; Wang, Kai-Fen; Caucci, Cherilyn; Tang, Shuo; Holland, Claire; Loercher, Amy; Gunn, George R

2018-03-16

Bridging immunoassays commonly used to detect and characterize immunogenicity during biologic development do not provide direct information on the presence or development of a memory anti-drug antibody (ADA) response. In this study, a B cell ELISPOT assay method was used to evaluate pre-existing ADA for anti-TNFR1 domain antibody, GSK1995057, an experimental biologic in treatment naive subjects. This assay utilized a 7-day activation of PBMCs by a combination of GSK1995057 (antigen) and polyclonal stimulator followed by GSK1995057-specific ELISPOT for the enumeration of memory B cells that have differentiated into antibody secreting cells (ASC) in vitro. We demonstrated that GSK1995057-specific ASC were detectable in treatment-naïve subjects with pre-existing ADA; the frequency of drug-specific ASC was low and ranged from 1 to 10 spot forming units (SFU) per million cells. Interestingly, the frequency of drug-specific ASC correlated with the ADA level measured using an in vitro ADA assay. We further confirmed that the ASC originated from CD27 + memory B cells, not from CD27 - -naïve B cells. Our data demonstrated the utility of the B cell ELISPOT method in therapeutic protein immunogenicity evaluation, providing a novel way to confirm and characterize the cell population producing pre-existing ADA. This novel application of a B cell ELISPOT assay informs and characterizes immune memory activity regarding incidence and magnitude associated with a pre-existing ADA response.

Semi-permeable coatings fabricated from comb-polymers efficiently protect proteins in vivo

NASA Astrophysics Data System (ADS)

Liu, Mi; Johansen, Pål; Zabel, Franziska; Leroux, Jean-Christophe; Gauthier, Marc A.

2014-11-01

In comparison to neutral linear polymers, functional and architecturally complex (that is, non-linear) polymers offer distinct opportunities for enhancing the properties and performance of therapeutic proteins. However, understanding how to harness these parameters is challenging, and studies that capitalize on them in vivo are scarce. Here we present an in vivo demonstration that modification of a protein with a polymer of appropriate architecture can impart low immunogenicity, with a commensurably low loss of therapeutic activity. These combined properties are inaccessible by conventional strategies using linear polymers. For the model protein L-asparaginase, a comb-polymer bio-conjugate significantly outperformed the linear polymer control in terms of lower immune response and more sustained bioactivity. The semi-permeability characteristics of the coatings are consistent with the phase diagram of the polymer, which will facilitate the application of this strategy to other proteins and with other therapeutic models.

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

NASA Astrophysics Data System (ADS)

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-04-01

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation

PubMed Central

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-01-01

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors’ knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability. PMID:27080134

A multiple-shape memory polymer-metal composite actuator capable of programmable control, creating complex 3D motion of bending, twisting, and oscillation.

PubMed

Shen, Qi; Trabia, Sarah; Stalbaum, Tyler; Palmre, Viljar; Kim, Kwang; Oh, Il-Kwon

2016-04-15

Development of biomimetic actuators has been an essential motivation in the study of smart materials. However, few materials are capable of controlling complex twisting and bending deformations simultaneously or separately using a dynamic control system. Here, we report an ionic polymer-metal composite actuator having multiple-shape memory effect, and is able to perform complex motion by two external inputs, electrical and thermal. Prior to the development of this type of actuator, this capability only could be realized with existing actuator technologies by using multiple actuators or another robotic system. This paper introduces a soft multiple-shape-memory polymer-metal composite (MSMPMC) actuator having multiple degrees-of-freedom that demonstrates high maneuverability when controlled by two external inputs, electrical and thermal. These multiple inputs allow for complex motions that are routine in nature, but that would be otherwise difficult to obtain with a single actuator. To the best of the authors' knowledge, this MSMPMC actuator is the first solitary actuator capable of multiple-input control and the resulting deformability and maneuverability.

An annulus fibrosus closure device based on a biodegradable shape-memory polymer network.

PubMed

Sharifi, Shahriar; van Kooten, Theo G; Kranenburg, Hendrik-Jan C; Meij, Björn P; Behl, Marc; Lendlein, Andreas; Grijpma, Dirk W

2013-11-01

Injuries to the intervertebral disc caused by degeneration or trauma often lead to tearing of the annulus fibrosus (AF) and extrusion of the nucleus pulposus (NP). This can compress nerves and cause lower back pain. In this study, the characteristics of poly(D,L-lactide-co-trimethylene carbonate) networks with shape-memory properties have been evaluated in order to prepare biodegradable AF closure devices that can be implanted minimally invasively. Four different macromers with (D,L-lactide) to trimethylene carbonate (DLLA:TMC) molar ratios of 80:20, 70:30, 60:40 and 40:60 with terminal methacrylate groups and molecular weights of approximately 30 kg mol(-1) were used to prepare the networks by photo-crosslinking. The mechanical properties of the samples and their shape-memory properties were determined at temperatures of 0 °C and 40 °C by tensile tests- and cyclic, thermo-mechanical measurements. At 40 °C all networks showed rubber-like behavior and were flexible with elastic modulus values of 1.7-2.5 MPa, which is in the range of the modulus values of human annulus fibrosus tissue. The shape-memory characteristics of the networks were excellent with values of the shape-fixity and the shape-recovery ratio higher than 98 and 95%, respectively. The switching temperatures were between 10 and 39 °C. In vitro culture and qualitative immunocytochemistry of human annulus fibrosus cells on shape-memory films with DLLA:TMC molar ratios of 60:40 showed very good ability of the networks to support the adhesion and growth of human AF cells. When the polymer network films were coated by adsorption of fibronectin, cell attachment, cell spreading, and extracellular matrix production was further improved. Annulus fibrosus closure devices were prepared from these AF cell-compatible materials by photo-polymerizing the reactive precursors in a mold. Insertion of the multifunctional implant in the disc of a cadaveric canine spine showed that these shape-memory devices could be

Polymers in the gut compress the colonic mucus hydrogel.

PubMed

Datta, Sujit S; Preska Steinberg, Asher; Ismagilov, Rustem F

2016-06-28

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host-microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer-mucus interactions can be described using a thermodynamic model based on Flory-Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice-whose microbiota degrade gut polymers-did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes.

Heparin-Mimicking Polymers: Synthesis and Biological Applications

PubMed Central

2016-01-01

Heparin is a naturally occurring, highly sulfated polysaccharide that plays a critical role in a range of different biological processes. Therapeutically, it is mostly commonly used as an injectable solution as an anticoagulant for a variety of indications, although it has also been employed in other forms such as coatings on various biomedical devices. Due to the diverse functions of this polysaccharide in the body, including anticoagulation, tissue regeneration, anti-inflammation, and protein stabilization, and drawbacks of its use, analogous heparin-mimicking materials are also widely studied for therapeutic applications. This review focuses on one type of these materials, namely, synthetic heparin-mimicking polymers. Utilization of these polymers provides significant benefits compared to heparin, including enhancing therapeutic efficacy and reducing side effects as a result of fine-tuning heparin-binding motifs and other molecular characteristics. The major types of the various polymers are summarized, as well as their applications. Because development of a broader range of heparin-mimicking materials would further expand the impact of these polymers in the treatment of various diseases, future directions are also discussed. PMID:27739666

Heparin-Mimicking Polymers: Synthesis and Biological Applications.

PubMed

Paluck, Samantha J; Nguyen, Thi H; Maynard, Heather D

2016-11-14

Heparin is a naturally occurring, highly sulfated polysaccharide that plays a critical role in a range of different biological processes. Therapeutically, it is mostly commonly used as an injectable solution as an anticoagulant for a variety of indications, although it has also been employed in other forms such as coatings on various biomedical devices. Due to the diverse functions of this polysaccharide in the body, including anticoagulation, tissue regeneration, anti-inflammation, and protein stabilization, and drawbacks of its use, analogous heparin-mimicking materials are also widely studied for therapeutic applications. This review focuses on one type of these materials, namely, synthetic heparin-mimicking polymers. Utilization of these polymers provides significant benefits compared to heparin, including enhancing therapeutic efficacy and reducing side effects as a result of fine-tuning heparin-binding motifs and other molecular characteristics. The major types of the various polymers are summarized, as well as their applications. Because development of a broader range of heparin-mimicking materials would further expand the impact of these polymers in the treatment of various diseases, future directions are also discussed.

Exploring 'new' bioactivities of polymers at the nano-bio interface.

PubMed

Wang, Chunming; Dong, Lei

2015-01-01

A biological system is essentially an elegant assembly of polymeric nanostructures. The polymers in the body, biomacromolecules, are both building blocks and versatile messengers. We propose that non-biologically derived polymers can be potential therapeutic candidates with unique advantages. Emerging findings about polycations, polysaccharides, immobilised multivalent ligands, and biomolecular coronas provide evidence that polymers are activated at the nano-bio interface, while emphasising the current theoretical and practical challenges. Our increasing understanding of the nano-bio interface and evolving approaches to establish the therapeutic potential of polymers enable the development of polymer drugs with high specificities for broad applications. Copyright © 2014 Elsevier Ltd. All rights reserved.

Potential Therapeutic Effects of Lipoic Acid on Memory Deficits Related to Aging and Neurodegeneration

PubMed Central

Molz, Patrícia; Schröder, Nadja

2017-01-01

The aging process comprises a series of organic alterations, affecting multiple systems, including the nervous system. Aging has been considered the main risk factor for the advance of neurodegenerative diseases, many of which are accompanied by cognitive impairment. Aged individuals show cognitive decline, which has been associated with oxidative stress, as well as mitochondrial, and consequently energetic failure. Lipoic acid (LA), a natural compound present in food and used as a dietary supplement, has been considered a promising agent for the treatment and/or prevention of neurodegenerative disorders. In spite of a number of preclinical studies showing beneficial effects of LA in memory functioning, and pointing to its neuroprotective potential effect, to date only a few studies have examined its effects in humans. Investigations performed in animal models of memory loss associated to aging and neurodegenerative disorders have shown that LA improves memory in a variety of behavioral paradigms. Moreover, cell and molecular mechanisms underlying LA effects have also been investigated. Accordingly, LA displays antioxidant, antiapoptotic, and anti-inflammatory properties in both in vivo and in vitro studies. In addition, it has been shown that LA reverses age-associated loss of neurotransmitters and their receptors, which can underlie its effects on cognitive functions. The present review article aimed at summarizing and discussing the main studies investigating the effects of LA on cognition as well as its cell and molecular effects, in order to improve the understanding of the therapeutic potential of LA on memory loss during aging and in patients suffering from neurodegenerative disorders, supporting the development of clinical trials with LA. PMID:29311912

Shape-memory surfaces for cell mechanobiology

PubMed Central

Ebara, Mitsuhiro

2015-01-01

Shape-memory polymers (SMPs) are a new class of smart materials, which have the capability to change from a temporary shape ‘A’ to a memorized permanent shape ‘B’ upon application of an external stimulus. In recent years, SMPs have attracted much attention from basic and fundamental research to industrial and practical applications due to the cheap and efficient alternative to well-known metallic shape-memory alloys. Since the shape-memory effect in SMPs is not related to a specific material property of single polymers, the control of nanoarchitecture of polymer networks is particularly important for the smart functions of SMPs. Such nanoarchitectonic approaches have enabled us to further create shape-memory surfaces (SMSs) with tunable surface topography at nano scale. The present review aims to bring together the exciting design of SMSs and the ever-expanding range of their uses as tools to control cell functions. The goal for these endeavors is to mimic the surrounding mechanical cues of extracellular environments which have been considered as critical parameters in cell fate determination. The untapped potential of SMSs makes them one of the most exciting interfaces of materials science and cell mechanobiology. PMID:27877747

Therapeutic and prophylactic utility of the memory-enhancing drug donepezil hydrochloride on cognition of patients undergoing electroconvulsive therapy: a randomized controlled trial.

PubMed

Prakash, Jyoti; Kotwal, Atul; Prabhu, Hra

2006-09-01

Substantial progress has been made in identifying how the treatment parameters used in electroconvulsive therapy (ECT) impact its cognitive side effects. However, there is limited information regarding the role of memory enhancers in post-ECT cognitive disturbances. We evaluated the therapeutic and prophylactic efficacy of the memory-enhancing drug donepezil hydrochloride on cognition of patients undergoing ECT. A triple blind (the study subjects, clinician assessing the cognition, and the data analyst were unaware of subject allocation for trial assessment) randomized controlled trial was carried out in a General Hospital Psychiatry Unit. Subjects were randomized into 2 groups. One group received ECT with placebo, whereas the other group received ECT and donepezil (a memory-enhancing drug). Study participants were assessed in post-ECT period to analyze cognitive deficits and to compare the differences in 2 groups, as regards recovery of various aspects of cognition. The post-ECT recovery of various components of cognition was more rapid in patients using donepezil as compared to those not given donepezil (P < 0.05). This significant improvement in recovery time among patients receiving donepezil bears therapeutic implication in immediate post-ECT cognitive deficits.

S 17092: a prolyl endopeptidase inhibitor as a potential therapeutic drug for memory impairment. Preclinical and clinical studies.

PubMed

Morain, Philippe; Lestage, Pierre; De Nanteuil, Guillaume; Jochemsen, Roeline; Robin, Jean-Loïc; Guez, David; Boyer, Pierre-Alain

2002-01-01

Any treatment that could positively modulate central neuropeptides levels would provide a promising therapeutic approach to the treatment of cognitive deficits associated with aging and/or neurodegenerative diseases. Therefore, based on the activity in rodents, S 17092 (2S,3aS,7aS)-1][(R,R)-2-phenylcyclopropyl]carbonyl]-2-[(thiazolidin-3-yl)carbonyl]octahydro-1H-indole) has been selected as a potent inhibitor of cerebral prolyl-endopeptidase (PEP). By retarding the degradation of neuroactive peptides, S 17092 was successfully used in a variety of memory tasks. These tasks explored short-term, long-term, reference and working memory in aged mice, as well as in rodents and monkeys with chemically induced amnesia or spontaneous memory deficits. S 17092 has also been safely administered to humans, and showed a clear peripheral expression of its mechanism of action through its inhibitory effect upon PEP activity in plasma. S 17092 exhibited central effects, as evidenced by EEG recording in healthy volunteers, and could improve a delayed verbal memory task. Collectively, the preclinical and clinical effects of S 17092 have suggested a promising role for this compound as an agent for the treatment of cognitive disorders associated with cerebral aging.

Virtual Treatment of Basilar Aneurysms Using Shape Memory Polymer Foam

NASA Astrophysics Data System (ADS)

Ortega, J. M.; Hartman, J.; Rodriguez, J. N.; Maitland, D. J.

2012-11-01

Numerical simulations are performed on patient-specific basilar aneurysms that are treated with shape memory polymer (SMP) foam. In order to assess the post-treatment hemodynamics, two modeling approaches are employed. In the first, the foam geometry is obtained from a micro-CT scan and the pulsatile blood flow within the foam is simulated for both Newtonian and non-Newtonian viscosity models. In the second, the foam is represented as a porous media continuum, which has permeability properties that are determined by computing the pressure gradient through the foam geometry over a range of flow speeds comparable to those of in vivo conditions. Virtual angiography and additional post-processing demonstrate that the SMP foam significantly reduces the blood flow speed within the treated aneurysms, while eliminating the high-frequency velocity fluctuations that are present prior to treatment. A prediction of the initial locations of thrombus formation throughout the SMP foam is obtained by means of a low fidelity thrombosis model that is based upon the residence time and shear rate of blood. The two modeling approaches capture similar qualitative trends for the initial locations of thrombus within the SMP foam.

Ferroelectric polarization induces electronic nonlinearity in ion-doped conducting polymers

PubMed Central

Fabiano, Simone; Sani, Negar; Kawahara, Jun; Kergoat, Loïg; Nissa, Josefin; Engquist, Isak; Crispin, Xavier; Berggren, Magnus

2017-01-01

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is an organic mixed ion-electron conducting polymer. The PEDOT phase transports holes and is redox-active, whereas the PSS phase transports ions. When PEDOT is redox-switched between its semiconducting and conducting state, the electronic and optical properties of its bulk are controlled. Therefore, it is appealing to use this transition in electrochemical devices and to integrate those into large-scale circuits, such as display or memory matrices. Addressability and memory functionality of individual devices, within these matrices, are typically achieved by nonlinear current-voltage characteristics and bistability—functions that can potentially be offered by the semiconductor-conductor transition of redox polymers. However, low conductivity of the semiconducting state and poor bistability, due to self-discharge, make fast operation and memory retention impossible. We report that a ferroelectric polymer layer, coated along the counter electrode, can control the redox state of PEDOT. The polarization switching characteristics of the ferroelectric polymer, which take place as the coercive field is overcome, introduce desired nonlinearity and bistability in devices that maintain PEDOT in its highly conducting and fast-operating regime. Memory functionality and addressability are demonstrated in ferro-electrochromic display pixels and ferro-electrochemical transistors. PMID:28695197

Transparent photostable ZnO nonvolatile memory transistor with ferroelectric polymer and sputter-deposited oxide gate

NASA Astrophysics Data System (ADS)

Park, C. H.; Im, Seongil; Yun, Jungheum; Lee, Gun Hwan; Lee, Byoung H.; Sung, Myung M.

2009-11-01

We report on the fabrication of transparent top-gate ZnO nonvolatile memory thin-film transistors (NVM-TFTs) with 200 nm thick poly(vinylidene fluoride/trifluoroethylene) ferroelectric layer; semitransparent 10 nm thin AgOx and transparent 130 nm thick indium-zinc oxide (IZO) were deposited on the ferroelectric polymer as gate electrode by rf sputtering. Our semitransparent NVM-TFT with AgOx gate operates under low voltage write-erase (WR-ER) pulse of ±20 V, but shows some degradation in retention property. In contrast, our transparent IZO-gated device displays very good retention properties but requires anomalously higher pulse of ±70 V for WR and ER states. Both devices stably operated under visible illuminations.

A constitutive theory for shape memory polymers: coupling of small and large deformation

NASA Astrophysics Data System (ADS)

Tan, Qiao; Liu, Liwu; Liu, Yanju; Leng, Jinsong; Yan, Xiangqiao; Wang, Haifang

2013-04-01

At high temperatures, SMPs share attributes like rubber and exhibit long-range reversibility. In contrast, at low temperatures they become very rigid and are susceptible to plastic, only small strains are allowable. But there relatively little literature has considered the unique small stain (rubber phase) and large stain (glass phase) coupling in SMPs when developing the constitutive modeling. In this work, we present a 3D constitutive model for shape memory polymers in both low temperature small strain regime and high temperature large strain regime. The theory is based on the work of Liu et al. [15]. Four steps of SMP's thermomechanical loadings cycle are considered in the constitutive model completely. The linear elastic and hyperelastic effects of SMP in different temperatures are also fully accounted for in the proposed model by adopt the neo-Hookean model and the Generalized Hooke's laws.

How music training enhances working memory: a cerebrocerebellar blending mechanism that can lead equally to scientific discovery and therapeutic efficacy in neurological disorders.

PubMed

Vandervert, Larry

2015-01-01

Following in the vein of studies that concluded that music training resulted in plastic changes in Einstein's cerebral cortex, controlled research has shown that music training (1) enhances central executive attentional processes in working memory, and (2) has also been shown to be of significant therapeutic value in neurological disorders. Within this framework of music training-induced enhancement of central executive attentional processes, the purpose of this article is to argue that: (1) The foundational basis of the central executive begins in infancy as attentional control during the establishment of working memory, (2) In accordance with Akshoomoff, Courchesne and Townsend's and Leggio and Molinari's cerebellar sequence detection and prediction models, the rigors of volitional control demands of music training can enhance voluntary manipulation of information in thought and movement, (3) The music training-enhanced blending of cerebellar internal models in working memory as can be experienced as intuition in scientific discovery (as Einstein often indicated) or, equally, as moments of therapeutic advancement toward goals in the development of voluntary control in neurological disorders, and (4) The blending of internal models as in (3) thus provides a mechanism by which music training enhances central executive processes in working memory that can lead to scientific discovery and improved therapeutic outcomes in neurological disorders. Within the framework of Leggio and Molinari's cerebellar sequence detection model, it is determined that intuitive steps forward that occur in both scientific discovery and during therapy in those with neurological disorders operate according to the same mechanism of adaptive error-driven blending of cerebellar internal models. It is concluded that the entire framework of the central executive structure of working memory is a product of the cerebrocerebellar system which can, through the learning of internal models

Artificial muscles made of chiral two-way shape memory polymer fibers

NASA Astrophysics Data System (ADS)

Yang, Qianxi; Fan, Jizhou; Li, Guoqiang

2016-10-01

In this work, we demonstrate the unusual improvement of the tensile actuation of hierarchically chiral structured artificial muscle made of two-way shape memory polymer (2W-SMP) fiber. Experimental results show that the chemically cross-linked poly(ethylene-co-vinyl acetate) 2W-SMP fibers possess an average negative coefficient of thermal expansion (NCTE) that is at least one order higher than that of the polyethylene fiber used previously. As expected, the increase in axial thermal contraction of the precursor fiber leads to an increase in the recovered torque ( 4.4 Nmm ) of the chiral fiber and eventually in the tensile actuation of the twisted-then-coiled artificial muscle ( 67.81 ±1.82 % ). A mechanical model based on Castigliano's second theorem is proposed, and the calculated result is consistent with the experimental result (64.17% tensile stroke). The model proves the significance of the NCTE and the recovered torque on tensile actuation of the artificial muscle and can be used as a guidance for the future design.

Surface modification of medical implant materials with hydrophilic polymers for enhanced biocompatibility and delivery of therapeutic agents

NASA Astrophysics Data System (ADS)

Urbaniak, Daniel J.

2004-11-01

In the research reported here, the surface modification of medical grade poly(dimethyl siloxane), polyetherurethane, and stainless steel through gamma-radiation grafting of hydrophilic polymers was investigated. Emphasis was placed on developing improved and simplified surface modification methods that produce more stable and more bioacceptible hydrophilic graft surfaces. As a result of this research, new surface modification techniques were developed that yield significantly improved surface stability unachievable using previous surface modification techniques. The surface modification of poly(dimethyl siloxane) with hydrophilic polymers was carried out using gamma radiation initiated graft polymerization. The addition of alkali metal hydroxides afforded a unique way to enhance the grafting of N-vinyl-2 pyrrolidone, dimethylacryamide, 2-methacryloyloxyethyl phosphoryl choline, N,N-dimethyl-N-(methacryloyloxyethyl)-N-(3-sulfopropyl)-ammonium-betaine, N,N-dimethyl-N-(methacrylamidopropyl)-N-(3-sulfopropyl)-ammonium-betaine, and copolymers thereof to silicones. Ethanolamine was found to further enhance the grafting of some hydrophilic polymers to silicone. The resulting hydrophilic surface grafts were resistant to hydrophobic surface rearrangement. This process overcomes previous problems inherent in silicone surface modification. The technique was also found to moderately enhance the grafting of hydrophilic monomers to polyetherurethane and to 316-L stainless steel. The surface modification of 316-L stainless steel was further enhanced by treating the substrates with a chromium III methacrylate bonding agent prior to irradiation. The coatings were evaluated for their potential use as depots for delivering therapeutic agents. The release of ofloxacin from surface-modified poly(dimethyl siloxane) and dexamethasone from surface-modified 316-L stainless steel was evaluated by in-vitro experiments. Therapeutic levels of drugs were released from surface-modified specimens

A shape memory polymer concrete crack closure system activated by electrical current

NASA Astrophysics Data System (ADS)

Teall, Oliver; Pilegis, Martins; Davies, Robert; Sweeney, John; Jefferson, Tony; Lark, Robert; Gardner, Diane

2018-07-01

The presence of cracks has a negative impact on the durability of concrete by providing paths for corrosive materials to the embedded steel reinforcement. Cracks in concrete can be closed using shape memory polymers (SMP) which produce a compressive stress across the crack faces. This stress has been previously found to enhance the load recovery associated with autogenous self-healing. This paper details the experiments undertaken to incorporate SMP tendons containing polyethylene terephthalate (PET) filaments into reinforced and unreinforced 500 × 100 × 100 mm structural concrete beam samples. These tendons are activated via an electrical supply using a nickel-chrome resistance wire heating system. The set-up, methodology and results of restrained shrinkage stress and crack closure experiments are explained. Crack closure of up to 85% in unreinforced beams and 26%–39% in reinforced beams is measured using crack-mouth opening displacement, microscope and digital image correlation equipment. Conclusions are made as to the effectiveness of the system and its potential for application within industry.

Self-Healing Composite of Thermoset Polymer and Programmed Super Contraction Fibers

NASA Technical Reports Server (NTRS)

Li, Guoqiang (Inventor); Meng, Harper (Inventor)

2016-01-01

A composition comprising thermoset polymer, shape memory polymer to facilitate macro scale damage closure, and a thermoplastic polymer for molecular scale healing is disclosed; the composition has the ability to resolve structural defects by a bio-mimetic close-then heal process. In use, the shape memory polymer serves to bring surfaces of a structural defect into approximation, whereafter use of the thermoplastic polymer for molecular scale healing allowed for movement of the thermoplastic polymer into the defect and thus obtain molecular scale healing. The thermoplastic can be fibers, particles or spheres which are used by heating to a level at or above the thermoplastic's melting point, then cooling of the composition below the melting temperature of the thermoplastic. Compositions of the invention have the ability to not only close macroscopic defects, but also to do so repeatedly even if another wound/damage occurs in a previously healed/repaired area.

Multi-shape memory polymers achieved by the spatio-assembly of 3D printable thermoplastic building blocks.

PubMed

Li, Hongze; Gao, Xiang; Luo, Yingwu

2016-04-07

Multi-shape memory polymers were prepared by the macroscale spatio-assembly of building blocks in this work. The building blocks were methyl acrylate-co-styrene (MA-co-St) copolymers, which have the St-block-(St-random-MA)-block-St tri-block chain sequence. This design ensures that their transition temperatures can be adjusted over a wide range by varying the composition of the middle block. The two St blocks at the chain ends can generate a crosslink network in the final device to achieve strong bonding force between building blocks and the shape memory capacity. Due to their thermoplastic properties, 3D printing was employed for the spatio-assembly to build devices. This method is capable of introducing many transition phases into one device and preparing complicated shapes via 3D printing. The device can perform a complex action via a series of shape changes. Besides, this method can avoid the difficult programing of a series of temporary shapes. The control of intermediate temporary shapes was realized via programing the shapes and locations of building blocks in the final device.

Geometry- and Length Scale-Dependent Deformation and Recovery on Micro- and Nanopatterned Shape Memory Polymer Surfaces

PubMed Central

Lee, Wei Li; Low, Hong Yee

2016-01-01

Micro- and nanoscale surface textures, when optimally designed, present a unique approach to improve surface functionalities. Coupling surface texture with shape memory polymers may generate reversibly tuneable surface properties. A shape memory polyetherurethane is used to prepare various surface textures including 2 μm- and 200 nm-gratings, 250 nm-pillars and 200 nm-holes. The mechanical deformation via stretching and recovery of the surface texture are investigated as a function of length scales and shapes. Results show the 200 nm-grating exhibiting more deformation than 2 μm-grating. Grating imparts anisotropic and surface area-to-volume effects, causing different degree of deformation between gratings and pillars under the same applied macroscopic strain. Full distribution of stress within the film causes the holes to deform more substantially than the pillars. In the recovery study, unlike a nearly complete recovery for the gratings after 10 transformation cycles, the high contribution of surface energy impedes the recovery of holes and pillars. The surface textures are shown to perform a switchable wetting function. This study provides insights into how geometric features of shape memory surface patterns can be designed to modulate the shape programming and recovery, and how the control of reversibly deformable surface textures can be applied to transfer microdroplets. PMID:27026290

Poly(Capro-Lactone) Networks as Actively Moving Polymers

NASA Astrophysics Data System (ADS)

Meng, Yuan

Shape-memory polymers (SMPs), as a subset of actively moving polymers, form an exciting class of materials that can store and recover elastic deformation energy upon application of an external stimulus. Although engineering of SMPs nowadays has lead to robust materials that can memorize multiple temporary shapes, and can be triggered by various stimuli such as heat, light, moisture, or applied magnetic fields, further commercialization of SMPs is still constrained by the material's incapability to store large elastic energy, as well as its inherent one-way shape-change nature. This thesis develops a series of model semi-crystalline shape-memory networks that exhibit ultra-high energy storage capacity, with accurately tunable triggering temperature; by introducing a second competing network, or reconfiguring the existing network under strained state, configurational chain bias can be effectively locked-in, and give rise to two-way shape-actuators that, in the absence of an external load, elongates upon cooling and reversibly contracts upon heating. We found that well-defined network architecture plays essential role on strain-induced crystallization and on the performance of cold-drawn shape-memory polymers. Model networks with uniform molecular weight between crosslinks, and specified functionality of each net-point, results in tougher, more elastic materials with a high degree of crystallinity and outstanding shape-memory properties. The thermal behavior of the model networks can be finely modified by introducing non-crystalline small molecule linkers that effectively frustrates the crystallization of the network strands. This resulted in shape-memory networks that are ultra-sensitive to heat, as deformed materials can be efficiently triggered to revert to its permanent state upon only exposure to body temperature. We also coupled the same reaction adopted to create the model network with conventional free-radical polymerization to prepare a dual-cure "double

Memory loss in Alzheimer's disease: implications for development of therapeutics

PubMed Central

Gold, Carl A; Budson, Andrew E

2009-01-01

Alzheimer's disease (AD) is a progressive neurodegenerative disease marked by a constellation of cognitive disturbances, the earliest and most prominent being impaired episodic memory. Episodic memory refers to the memory system that allows an individual to consciously retrieve a previously experienced item or episode of life. Many recent studies have focused on characterizing how AD pathology impacts particular aspects of episodic memory and underlying mental and neural processes. This review summarizes the findings of those studies and discusses the effects of current and promising treatments for AD on episodic memory. The goal of this review is to raise awareness of the strides that cognitive neuroscientists have made in understanding intact and dysfunctional memory. Knowledge of the specific memorial processes that are impaired in AD may be of great value to basic scientists developing novel therapies and to clinical researchers assessing the efficacy of those therapies. PMID:19086882

Effect of Biodegradable Shape-Memory Polymers on Proliferation of 3T3 Cells

NASA Astrophysics Data System (ADS)

Xu, Shuo-Gui; Zhang, Peng; Zhu, Guang-Ming; Jiang, Ying-Ming

2011-07-01

This article evaluates the in vitro biocompatibility for biodegradable shape-memory polymers (BSMP) invented by the authors. 3T3 cells (3T3-Swiss albino GNM 9) of primary and passaged cultures were inoculated into two kinds of carriers: the BSMP carrier and the control group carrier. Viability, proliferation, and DNA synthesis (the major biocompatibility parameters), were measured and evaluated for both the BSMP and naked carrier via cell growth curve analysis, MTT colorimetry and addition of 3H-TdR to culture media. The results showed that there was no difference between the BSMP carrier and the control dish in terms of viability, proliferation, and metabolism of the 3T3 cells. Overall, the BSMP carrier provides good biocompatibility and low toxicity to cells in vitro, and could indicate future potential for this medium as a biological material for implants in vivo.

Characterization of Therapeutic Coatings on Medical Devices

NASA Astrophysics Data System (ADS)

Wormuth, Klaus

Therapeutic coatings on medical devices such as catheters, guide wires, and stents improve biocompatibility by favorably altering the chemical nature of the device/tissue or device/blood interface. Such coatings often minimize tissue damage (reduce friction), decrease chances for blood clot formation (prevent platelet adsorption), and improve the healing response (deliver drugs). Confocal Raman microscopy provides valuable information about biomedical coatings by, for example, facilitating the measurement of the thickness and swelling of frictionreducing hydrogel coatings on catheters and by determining the distribution of drug within a polymer-based drug-eluting coatings on stents. This chapter explores the application of Raman microscopy to the imaging of thin coatings of cross-linked poly(vinyl pyrrolidone) gels, parylene films, mixtures of dexamethasone with various polymethacrylates, and mixtures of rapamycin with hydrolysable (biodegradable) poly(lactide-co-glycolide) polymers. Raman microscopy measures the thickness and swelling of coatings, reveals the degree of mixing of drug and polymer, senses the hydrolysis of biodegradable polymers, and determines the polymorphic forms of drug present within thin therapeutic coatings on medical devices.

Synthesis and characterization of shape memory poly (epsilon-caprolactone) polyurethane-ureas

NASA Astrophysics Data System (ADS)

Ren, Hongfeng

Shape memory polymers (SMPs) have attracted significant interest in recent times because of their potential applications in a number of areas, such as medical devices and textiles. However, there are some major drawbacks of SMPs, such as their relatively low moduli resulting in small recovery stresses, and their long response times compared with shape memory alloys (SMAs). A suitable recovery stress which comes from the elastic recovery stress generated in the deformation process is critical in some medical devices. To address some of these shortcomings, the work in this dissertation mainly focuses on the design and synthesis of linear shape memory polymers with higher recovery stress. A series of segmented poly (epsilon-caprolactone) polyurethane-ureas (PCLUUs) were prepared from poly (epsilon-caprolactone) (PCL) diol, different dissociates and chain extenders. NMR and FT-IR were used to identify the structure of the synthesized shape memory polyurethane-ureas. Parameters such as soft segment content (molecular weight and content), chain extender and the rigidity of the main chain were investigated to understand the structure-property relationships of the shape memory polymer systems through DSC, DMA, physical property test, etc. Cyclic thermal mechanic tests were applied to measure the shape memory properties which showed that the recovery stress can be improved above 200% simply by modifying the chain extender. Meanwhile, the synthesis process was optimized to be similar to that of Spandex /LYCRA®. Continuous fibers form shape memory polyurethane-ureas were made from a wet spinning process, which indicated excellent spinnability of the polymer solution. Small angle neutron scattering (SANS) was used to study the morphology of the hard segment at different temperatures and stretch rates and found that the monodisperse rigid cylinder model fit the SANS data quite well. From the cylinder model, the radius of the cylinder increased with increasing hard segment

Thermomechanical properties of polyurethane shape memory polymer-experiment and modelling

NASA Astrophysics Data System (ADS)

Pieczyska, E. A.; Maj, M.; Kowalczyk-Gajewska, K.; Staszczak, M.; Gradys, A.; Majewski, M.; Cristea, M.; Tobushi, H.; Hayashi, S.

2015-04-01

In this paper extensive research on the polyurethane shape memory polymer (PU-SMP) is reported, including its structure analysis, our experimental investigation of its thermomechanical properties and its modelling. The influence of the effects of thermomechanical couplings on the SMP behaviour during tension at room temperature is studied using a fast and sensitive infrared camera. It is shown that the thermomechanical behaviour of the SMP significantly depends on the strain rate: at a higher strain rate higher stress and temperature values are obtained. This indicates that an increase of the strain rate leads to activation of different deformation mechanisms at the micro-scale, along with reorientation and alignment of the molecular chains. Furthermore, influence of temperature on the SMP’s mechanical behaviour is studied. It is observed during the loading in a thermal chamber that at the temperature 20 °C below the glass transition temperature (Tg) the PU-SMP strengthens about six times compared to the material above Tg but does not exhibit the shape recovery. A finite-strain constitutive model is formulated, where the SMP is described as a two-phase material composed of a hyperelastic rubbery phase and elastic-viscoplastic glassy phase. The volume content of phases is governed by the current temperature. Finally, model predictions are compared with the experimental results.

Micro devices using shape memory polymer patches for mated connections

DOEpatents

Lee, Abraham P.; Fitch, Joseph P.

2000-01-01

A method and micro device for repositioning or retrieving miniature devices located in inaccessible areas, such as medical devices (e.g., stents, embolic coils, etc.) located in a blood vessel. The micro repositioning or retrieving device and method uses shape memory polymer (SMP) patches formed into mating geometries (e.g., a hoop and a hook) for re-attachment of the deposited medical device to a catheter or guidewire. For example, SMP or other material hoops are formed on the medical device to be deposited in a blood vessel, and SMP hooks are formed on the micro device attached to a guidewire, whereby the hooks on the micro device attach to the hoops on the medical device, or vice versa, enabling deposition, movement, re-deposit, or retrieval of the medical device. By changing the temperature of the SMP hooks, the hooks can be attached to or released from the hoops located on the medical device. An exemplary method for forming the hooks and hoops involves depositing a sacrificial thin film on a substrate, patterning and processing the thin film to form openings therethrough, depositing or bonding SMP materials in the openings so as to be attached to the substrate, and removing the sacrificial thin film.

Virtual Treatment of Basilar Aneurysms Using Shape Memory Polymer Foam

PubMed Central

Ortega, J.M.; Hartman, J.; Rodriguez, J.N.; Maitland, D.J.

2013-01-01

Numerical simulations are performed on patient-specific basilar aneurysms that are treated with shape memory polymer (SMP) foam. In order to assess the post-treatment hemodynamics, two modeling approaches are employed. In the first, the foam geometry is obtained from a micro-CT scan and the pulsatile blood flow within the foam is simulated for both Newtonian and non-Newtonian viscosity models. In the second, the foam is represented as a porous media continuum, which has permeability properties that are determined by computing the pressure gradient through the foam geometry over a range of flow speeds comparable to those of in vivo conditions. Virtual angiography and additional post-processing demonstrate that the SMP foam significantly reduces the blood flow speed within the treated aneurysms, while eliminating the high-frequency velocity fluctuations that are present within the pre-treatment aneurysms. An estimation of the initial locations of thrombus formation throughout the SMP foam is obtained by means of a low fidelity thrombosis model that is based upon the residence time and shear rate of blood. The Newtonian viscosity model and the porous media model capture similar qualitative trends, though both yield a smaller volume of thrombus within the SMP foam. PMID:23329002

Polymers in the gut compress the colonic mucus hydrogel

PubMed Central

Datta, Sujit S.; Preska Steinberg, Asher

2016-01-01

Colonic mucus is a key biological hydrogel that protects the gut from infection and physical damage and mediates host–microbe interactions and drug delivery. However, little is known about how its structure is influenced by materials it comes into contact with regularly. For example, the gut abounds in polymers such as dietary fibers or administered therapeutics, yet whether such polymers interact with the mucus hydrogel, and if so, how, remains unclear. Although several biological processes have been identified as potential regulators of mucus structure, the polymeric composition of the gut environment has been ignored. Here, we demonstrate that gut polymers do in fact regulate mucus hydrogel structure, and that polymer–mucus interactions can be described using a thermodynamic model based on Flory–Huggins solution theory. We found that both dietary and therapeutic polymers dramatically compressed murine colonic mucus ex vivo and in vivo. This behavior depended strongly on both polymer concentration and molecular weight, in agreement with the predictions of our thermodynamic model. Moreover, exposure to polymer-rich luminal fluid from germ-free mice strongly compressed the mucus hydrogel, whereas exposure to luminal fluid from specific-pathogen-free mice—whose microbiota degrade gut polymers—did not; this suggests that gut microbes modulate mucus structure by degrading polymers. These findings highlight the role of mucus as a responsive biomaterial, and reveal a mechanism of mucus restructuring that must be integrated into the design and interpretation of studies involving therapeutic polymers, dietary fibers, and fiber-degrading gut microbes. PMID:27303035

Robust Vacuum-/Air-Dried Graphene Aerogels and Fast Recoverable Shape-Memory Hybrid Foams.

PubMed

Li, Chenwei; Qiu, Ling; Zhang, Baoqing; Li, Dan; Liu, Chen-Yang

2016-02-17

New graphene aerogels can be fabricated by vacuum/air drying, and because of the mechanical robustness of the graphene aerogels, shape-memory polymer/graphene hybrid foams can be fabricated by a simple infiltration-air-drying-crosslinking method. Due to the superelasticity, high strength, and good electrical conductivity of the as-prepared graphene aerogels, the shape-memory hybrid foams exhibit excellent thermotropical and electrical shape-memory properties, outperforming previously reported shape-memory polymer foams. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Attachment styles, memories of parental rearing and therapeutic bond: a study with eating disordered patients, their parents and therapists.

PubMed

Tereno, Susana; Soares, Isabel; Martins, Carla; Celani, Mariana; Sampaio, Daniel

2008-01-01

Patients diagnosed with anorexia nervosa (n = 30) and bulimia nervosa (n = 27), their parents and therapists were recruited for this study aimed at examining differences between clinical groups and a control group (n = 35) in terms of attachment styles and perceptions of memories of parental rearing. Within the clinical groups, relations among these variables and therapeutic bond were explored. In addition, parents' and their daughters' attachment styles were compared. The results showed differences between clinical and control groups: the daughters in the control group reported lower levels of attachment anxiety compared to those of the clinical groups; their mothers exhibited higher security than mothers of anorectic patients and lower avoidance than mothers of bulimic patients. For the anorectic group, therapeutic bond was associated to higher father's emotional support and lower rejection; in the bulimic group, therapeutic bond was related to higher maternal emotional support and lower rejection as well as to lower paternal overprotection.

A simplified constitutive model for predicting shape memory polymers deformation behavior

NASA Astrophysics Data System (ADS)

Li, Yunxin; Guo, Siu-Siu; He, Yuhao; Liu, Zishun

2015-12-01

Shape memory polymers (SMPs) can keep a temporary shape after pre-deformation at a higher temperature and subsequent cooling. When they are reheated, their original shapes can be recovered. Such special characteristics of SMPs make them widely used in aerospace structures, biomedical devices, functional textiles and other devices. Increasing usefulness of SMPs motivates us to further understand their thermomechanical properties and deformation behavior, of which the development of appropriate constitutive models for SMPs is imperative. There is much work in literatures that address constitutive models of the thermo-mechanical coupling in SMPs. However, due to their complex forms, it is difficult to apply these constitutive models in the real world. In this paper, a three-element model with simple form is proposed to investigate the thermo-mechanical small strain (within 10%) behavior of polyurethane under uniaxial tension. Two different cases of heated recovery are considered: (1) unconstrained free strain recovery and (2) stress recovery under full constraint at a strain level fixed during low temperature unloading. To validate the model, simulated and predicted results are compared with Tobushi's experimental results and good agreement can be observed.

Designing multifunctional polymers for cardiovascular implants.

PubMed

Wischke, Christian; Lendlein, Andreas

2011-01-01

Polymer-based biomaterials are extensively used in all disciplines of clinical medicine and innovations in biomaterial science are building a product pipeline, e.g., of future cardiovascular implants. Still, cardiovascular applications demand a number of extensive requirements of properties and functions to be fulfilled by the polymer matrix. This report provides an overview on some of these issues and how they can be addressed by a tailored design of novel polymer-based biomaterials. Multifunctional shape-memory polymers are highlighted as a class of materials that combine biocompatibility and the capability for stimuli-induced active movements for anchoring of implants with a controlled degradation and drug release profile to enable a functional regeneration of the tissue at the application site.

Inductively heated shape memory polymer for the magnetic actuation of medical devices.

PubMed

Buckley, Patrick R; McKinley, Gareth H; Wilson, Thomas S; Small, Ward; Benett, William J; Bearinger, Jane P; McElfresh, Michael W; Maitland, Duncan J

2006-10-01

Presently, there is interest in making medical devices such as expandable stents and intravascular microactuators from shape memory polymer (SMP). One of the key challenges in realizing SMP medical devices is the implementation of a safe and effective method of thermally actuating various device geometries in vivo. A novel scheme of actuation by Curie-thermoregulated inductive heating is presented. Prototype medical devices made from SMP loaded with nickel zinc ferrite ferromagnetic particles were actuated in air by applying an alternating magnetic field to induce heating. Dynamic mechanical thermal analysis was performed on both the particle-loaded and neat SMP materials to assess the impact of the ferrite particles on the mechanical properties of the samples. Calorimetry was used to quantify the rate of heat generation as a function of particle size and volumetric loading of ferrite particles in the SMP. These tests demonstrated the feasibility of SMP actuation by inductive heating. Rapid and uniform heating was achieved in complex device geometries and particle loading up to 10% volume content did not interfere with the shape recovery of the SMP.

Thermally Activated Composite with Two-Way and Multi-Shape Memory Effects

PubMed Central

Basit, Abdul; L’Hostis, Gildas; Pac, Marie José; Durand, Bernard

2013-01-01

The use of shape memory polymer composites is growing rapidly in smart structure applications. In this work, an active asymmetric composite called “controlled behavior composite material (CBCM)” is used as shape memory polymer composite. The programming and the corresponding initial fixity of the composite structure is obtained during a bending test, by heating CBCM above thermal glass transition temperature of the used Epoxy polymer. The shape memory properties of these composites are investigated by a bending test. Three types of recoveries are conducted, two classical recovery tests: unconstrained recovery and constrained recovery, and a new test of partial recovery under load. During recovery, high recovery displacement and force are produced that enables the composite to perform strong two-way actuations along with multi-shape memory effect. The recovery force confirms full recovery with two-way actuation even under a high load. This unique property of CBCM is characterized by the recovered mechanical work. PMID:28788316

Microfabricated therapeutic actuators and release mechanisms therefor

DOEpatents

Lee, Abraham P.; Fitch, Joseph P.; Schumann, Daniel L.; Da Silva, Luiz; Benett, William J.; Krulevitch, Peter A.

2000-01-01

Microfabricated therapeutic actuators are fabricated using a shape memory polymer (SMP), a polyurethane-based material that undergoes a phase transformation at a specified temperature (Tg). At a temperature above temperature Tg material is soft and can be easily reshaped into another configuration. As the temperature is lowered below temperature Tg the new shape is fixed and locked in as long as the material stays below temperature Tg. Upon reheating the material to a temperature above Tg, the material will return to its original shape. By the use of such SMP material, SMP microtubing can be used as a retaining/release actuator for the delivery of material, such as embolic coils, for example, through catheters into aneurysms, for example. The microtubing can be manufactured in various sizes and the phase change temperature Tg is determinate for an intended temperature target and intended use. The SMP microtubing can be positioned around or within an end of a deposit material. Various heating arrangements can be utilized with the SMP release mechanism, and the SMP microtubing can include a metallic coating for enhanced light absorption.

Plasma immersion ion implantation of polyurethane shape memory polymer: Surface properties and protein immobilization

NASA Astrophysics Data System (ADS)

Cheng, Xinying; Kondyurin, Alexey; Bao, Shisan; Bilek, Marcela M. M.; Ye, Lin

2017-09-01

Polyurethane-type shape memory polymers (SMPU) are promising biomedical implant materials due to their ability to recover to a predetermined shape from a temporary shape induced by thermal activation close to human body temperature and their advantageous mechanical properties including large recovery strains and low recovery stresses. Plasma Immersion Ion Implantation (PIII) is a surface modification process using energetic ions that generates radicals in polymer surfaces leading to carbonisation and oxidation and the ability to covalently immobilise proteins without the need for wet chemistry. Here we show that PIII treatment of SMPU significantly enhances its bioactivity making SMPU suitable for applications in permanent implantable biomedical devices. Scanning Electron Microscopy (SEM), contact angle measurements, surface energy measurements, attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were used to characterise the PIII modified surface, including its after treatment aging kinetics and its capability to covalently immobilise protein directly from solution. The results show a substantial improvement in wettability and dramatic changes of surface chemical composition dependent on treatment duration, due to the generation of radicals and subsequent oxidation. The SMPU surface, PIII treated for 200s, achieved a saturated level of covalently immobilized protein indicating that a full monolayer coverage was achieved. We conclude that PIII is a promising and efficient surface modification method to enhance the biocompatibility of SMPU for use in medical applications that demand bioactivity for tissue integration and stability in vivo.

Polymer-Based Therapeutics: Nanoassemblies and Nanoparticles for Management of Atherosclerosis

PubMed Central

Lewis, Daniel R.; Kamisoglu, Kubra; York, Adam; Moghe, Prabhas V.

2012-01-01

Coronary arterial disease, one of the leading causes of adult mortality, is triggered by atherosclerosis. A disease with complex etiology, atherosclerosis results from the progressive long-term combination of atherogenesis, the accumulation of modified lipoproteins within blood vessel walls, along with vascular and systemic inflammatory processes. The management of atherosclerosis is challenged by the localized flare-up of several multipronged signaling interactions between activated monocytes, atherogenic macrophages and inflamed or dysfunctional endothelial cells. A new generation of approaches is now emerging founded on multifocal, targeted therapies that seek to reverse or ameliorate the athero-inflammatory cascade within the vascular intima. This article reviews the various classes and primary examples of bioactive configurations of nanoscale assemblies. Of specific interest are polymer-based or polymer-lipid micellar assemblies designed as multimodal receptor-targeted blockers or drug carriers whose activity can be tuned by variations in polymer hydrophobicity, charge, and architecture. Also reviewed are emerging reports on multifunctional nanoassemblies and nanoparticles for improved circulation and enhanced targeting to athero-inflammatory lesions and atherosclerotic plaques. PMID:21523920

[Polymer and oligomer based doxorubicin carriers].

PubMed

Kik, Krzysztof; Lwow, Felicja; Szmigiero, Leszek

2007-01-01

Doxorubicin and other anthracycline derivatives play an important role in the treatment of many malignant diseases. Unfortunately, clinical effectiveness of this class of drugs is limited by cumulative cardiotoxicity which occurs in significant percentage of patients at cumulative dose in the range 450-600 mg/m2. Therefore, several strategies have been developed to reduce cardiotoxicity of doxorubicin and its analogues. One of the possible ways leading to the improvement of anticancer selectivity of doxorubicin is the design of polymer and olygomer carriers which may transport drug molecules more efficiently and more specifically. Synthetic polymers are of increasing interest as therapeutic agents owing to their enhanced pharmacokinetic profiles relative to small molecule drugs. Currently a new class of multifunctional polymers is being prepared that can "mask" biologically active compounds, such as cytotoxic agents, until they reach target sites, but which can then release the agent in situ to effect the therapy. The legitimacy of the development of polymer based doxorubicine carriers is supported by the growing number of clinical reports indicating that the use of hydrophilic polymers or polymer coated liposomes as a platform for delivery of the drug results in better therapeutic effects than the free drug. In this article we present the most promising strategies directed at the development of improved anthracycline drugs formulations based of polymer and olygomer carriers. We review: 1) polyethylenoglycol-coated ("pegylated") liposomal doxorubicin; 2) extracellulary tumor-activated prodrugs which are conjugates of doxorubicin with peptides; 3) doxorubicin coated by higly polymerised glycosoaminoglycans; 4) conjugates of doxorubicin with copolymer of N-(2-hydroxypropyl)methacrylamide.

Effects of thermo-mechanical behavior and hinge geometry on folding response of shape memory polymer sheets

NASA Astrophysics Data System (ADS)

Mailen, Russell W.; Dickey, Michael D.; Genzer, Jan; Zikry, Mohammed

2017-11-01

Shape memory polymer (SMP) sheets patterned with black ink hinges change shape in response to external stimuli, such as absorbed thermal energy from an infrared (IR) light. The geometry of these hinges, including size, orientation, and location, and the applied thermal loads significantly influence the final folded shape of the sheet, but these variables have not been fully investigated. We perform a systematic study on SMP sheets to fundamentally understand the effects of single and double hinge geometries, hinge orientation and spacing, initial temperature, heat flux intensity, and pattern width on the folding behavior. We have developed thermo-viscoelastic finite element models to characterize and quantify the stresses, strains, and temperatures as they relate to SMP shape changes. Our predictions indicate that hinge orientation can be used to reduce the total bending angle, which is the angle traversed by the folding face of the sheet. Two parallel hinges increase the total bending angle, and heat conduction between the hinges affects the transient folding response. IR intensity and initial temperatures can also influence the transient folding behavior. These results can provide guidelines to optimize the transient folding response and the three-dimensional folded structure obtained from self-folding polymer origami sheets that can be applied for myriad applications.

Surface-modified polymers for cardiac tissue engineering.

PubMed

Moorthi, Ambigapathi; Tyan, Yu-Chang; Chung, Tze-Wen

2017-09-26

Cardiovascular disease (CVD), leading to myocardial infarction and heart failure, is one of the major causes of death worldwide. The physiological system cannot significantly regenerate the capabilities of a damaged heart. The current treatment involves pharmacological and surgical interventions; however, less invasive and more cost-effective approaches are sought. Such new approaches are developed to induce tissue regeneration following injury. Hence, regenerative medicine plays a key role in treating CVD. Recently, the extrinsic stimulation of cardiac regeneration has involved the use of potential polymers to stimulate stem cells toward the differentiation of cardiomyocytes as a new therapeutic intervention in cardiac tissue engineering (CTE). The therapeutic potentiality of natural or synthetic polymers and cell surface interactive factors/polymer surface modifications for cardiac repair has been demonstrated in vitro and in vivo. This review will discuss the recent advances in CTE using polymers and cell surface interactive factors that interact strongly with stem cells to trigger the molecular aspects of the differentiation or formulation of cardiomyocytes for the functional repair of heart injuries or cardiac defects.

Anti-Cancer Drug Delivery Using Carbohydrate-Based Polymers.

PubMed

Ranjbari, Javad; Mokhtarzadeh, Ahad; Alibakhshi, Abbas; Tabarzad, Maryam; Hejazi, Maryam; Ramezani, Mohammad

2018-02-12

Polymeric drug delivery systems in the form of nanocarriers are the most interesting vehicles in anticancer therapy. Among different types of biocompatible polymers, carbohydrate-based polymers or polysaccharides are the most common natural polymers with complex structures consisting of long chains of monosaccharide or disaccharide units bound by glycosidic linkages. Their appealing properties such as availability, biocompatibility, biodegradability, low toxicity, high chemical reactivity, facile chemical modification and low cost led to their extensive applications in biomedical and pharmaceutical fields including development of nano-vehicles for delivery of anti-cancer therapeutic agents. Generally, reducing systemic toxicity, increasing short half-lives and tumor localization of agents are the top priorities for a successful cancer therapy. Polysaccharide-based or - coated nanosystems with respect to their advantageous features as well as accumulation in tumor tissue due to enhanced permeation and retention (EPR) effect can provide promising carrier systems for the delivery of noblest impressive agents. Most challenging factor in cancer therapy was the toxicity of anti-cancer therapeutic agents for normal cells and therefore, targeted delivery of these drugs to the site of action can be considered as an interesting therapeutic strategy. In this regard, several polysaccharides exhibited selective affinity for specific cell types, and so they can act as a targeting agent in drug delivery systems. Accordingly, different aspects of polysaccharide applications in cancer treatment or diagnosis were reviewed in this paper. In this regard, after a brief introduction of polysaccharide structure and its importance, the pharmaceutical usage of carbohydrate-based polymers was considered according to the identity of accompanying active pharmaceutical agents. It was also presented that the carbohydrate based polymers have been extensively considered as promising materials in

Development of a self-stressing NiTiNb shape memory alloy (SMA)/fiber reinforced polymer (FRP) patch

NASA Astrophysics Data System (ADS)

El-Tahan, M.; Dawood, M.; Song, G.

2015-06-01

The objective of this research is to develop a self-stressing patch using a combination of shape memory alloys (SMAs) and fiber reinforced polymer (FRP) composites. Prestressed carbon FRP patches are emerging as a promising alternative to traditional methods to repair cracked steel structures and civil infrastructure. However, prestressing these patches typically requires heavy and complex fixtures, which is impractical in many applications. This paper presents a new approach in which the prestressing force is applied by restraining the shape memory effect of NiTiNb SMA wires. The wires are subsequently embedded in an FRP overlay patch. This method overcomes the practical challenges associated with conventional prestressing. This paper presents the conceptual development of the self-stressing patch with the support of experimental observations. The bond between the SMA wires and the FRP is evaluated using pull-out tests. The paper concludes with an experimental study that evaluates the patch response during activation subsequent monotonic tensile loading. The results demonstrate that the self-stressing patch with NiTiNb SMA is capable of generating a significant prestressing force with minimal tool and labor requirements.

Dendritic polymer imaging systems for the evaluation of conjugate uptake and cleavage

NASA Astrophysics Data System (ADS)

Krüger, Harald R.; Nagel, Gregor; Wedepohl, Stefanie; Calderón, Marcelo

2015-02-01

Fluorescent turn-on probes combined with polymers have a broad range of applications, e.g. for intracellular sensing of ions, small molecules, or DNA. In the field of polymer therapeutics, these probes can be applied to extend the in vitro characterization of novel conjugates beyond cytotoxicity and cellular uptake studies. This is particularly true in cases in which polymer conjugates contain drugs attached by cleavable linkers. Better information on the intracellular linker cleavage and drug release would allow a faster evaluation and optimization of novel polymer therapeutic concepts. We therefore developed a fluorescent turn-on probe that enables direct monitoring of pH-mediated cleavage processes over time. This is achieved by exploiting the fluorescence resonance energy transfer (FRET) between two dyes that have been coupled to a dendritic polymer. We demonstrate the use of this probe to evaluate polymer uptake and intracellular release of cargo in a cell based microplate assay that is suitable for high throughput screening.Fluorescent turn-on probes combined with polymers have a broad range of applications, e.g. for intracellular sensing of ions, small molecules, or DNA. In the field of polymer therapeutics, these probes can be applied to extend the in vitro characterization of novel conjugates beyond cytotoxicity and cellular uptake studies. This is particularly true in cases in which polymer conjugates contain drugs attached by cleavable linkers. Better information on the intracellular linker cleavage and drug release would allow a faster evaluation and optimization of novel polymer therapeutic concepts. We therefore developed a fluorescent turn-on probe that enables direct monitoring of pH-mediated cleavage processes over time. This is achieved by exploiting the fluorescence resonance energy transfer (FRET) between two dyes that have been coupled to a dendritic polymer. We demonstrate the use of this probe to evaluate polymer uptake and intracellular

Biodegradable polymers for targeted delivery of anti-cancer drugs.

PubMed

Doppalapudi, Sindhu; Jain, Anjali; Domb, Abraham J; Khan, Wahid

2016-06-01

Biodegradable polymers have been used for more than three decades in cancer treatment and have received increased interest in recent years. A range of biodegradable polymeric drug delivery systems designed for localized and systemic administration of therapeutic agents as well as tumor-targeting macromolecules has entered into the clinical phase of development, indicating the significance of biodegradable polymers in cancer therapy. This review elaborates upon applications of biodegradable polymers in the delivery and targeting of anti-cancer agents. Design of various drug delivery systems based on biodegradable polymers has been described. Moreover, the indication of polymers in the targeted delivery of chemotherapeutic drugs via passive, active targeting, and localized drug delivery are also covered. Biodegradable polymer-based drug delivery systems have the potential to deliver the payload to the target and can enhance drug availability at desired sites. Systemic toxicity and serious side effects observed with conventional cancer therapeutics can be significantly reduced with targeted polymeric systems. Still, there are many challenges that need to be met with respect to the degradation kinetics of the system, diffusion of drug payload within solid tumors, targeting tumoral tissue and tumor heterogeneity.

Variable-Resistivity Material For Memory Circuits

NASA Technical Reports Server (NTRS)

Nagasubramanian, Ganesan; Distefano, Salvador; Moacanin, Jovan

1989-01-01

Nonvolatile memory elements packed densely. Electrically-erasable, programmable, read-only memory matrices made with newly-synthesized organic material of variable electrical resistivity. Material, polypyrrole doped with tetracyanoquinhydrone (TCNQ), changes reversibly between insulating or higher-resistivity state and conducting or low-resistivity state. Thin film of conductive polymer separates layer of row conductors from layer of column conductors. Resistivity of film at each intersection and, therefore, resistance of memory element defined by row and column, increased or decreased by application of suitable switching voltage. Matrix circuits made with this material useful for experiments in associative electronic memories based on models of neural networks.

Note: A simple picture of subdiffusive polymer motion from stochastic simulations

NASA Astrophysics Data System (ADS)

Gniewek, Pawel; Kolinski, Andrzej

2011-02-01

Entangled polymer solutions and melts exhibit unusual frictional properties. In the entanglement limit self-diffusion coefficient of long flexible polymers decays with the second power of chain length and viscosity increases with 3-3.5 power of chain length.1 It is very difficult to provide detailed molecular-level explanation of the entanglement effect.2 Perhaps, the problem of many entangled polymer chains is the most complex multibody issue of classical physics. There are different approaches to polymer melt dynamics. Some of these recognize hydrodynamic interactions as a dominant term, while topological constraints for polymer chains are assumed as a secondary factor. Other theories consider the topological constraints as the most important factors controlling polymer dynamics. Herman and co-workers describe polymer dynamics in melts, as a lateral sliding of a chain along other chains until complete mutual disentanglement. Despite the success in explaining the power-laws for viscosity, the model has some limitations. First of all, memory effects are ignored, that is, polymer segments are treated independently. Also, each entanglement/obstacle is treated as a separate entity, which is certainly a simplification of the memory effect problem. In addition to that, correlated motions of segments are addressed within the framework of renormalized Rouse-chain theory,7 without calling any topological entanglements in advance. This approach leads to the generalized Langevin equation characterized by distinct memory kernels describing local and nonlocal segment correlations or to the Smoluchowski equation in which the segments' mobility is treated as a stochastic variable.11 Both models describe the polymer segments motion at a microscopic level. An interesting alternative is to solve the integrodifferential equation for the chain relaxation with a sophisticated kernel function.12 The design of the kernel function is based on a mesoscopic description of the polymer melt

The quintuple-shape memory effect in electrospun nanofiber membranes

NASA Astrophysics Data System (ADS)

Zhang, Fenghua; Zhang, Zhichun; Liu, Yanju; Lu, Haibao; Leng, Jinsong

2013-08-01

Shape memory fibrous membranes (SMFMs) are an emerging class of active polymers, which are capable of switching from a temporary shape to their permanent shape upon appropriate stimulation. Quintuple-shape memory membranes based on the thermoplastic polymer Nafion, with a stable fibrous structure, are achieved via electrospinning technology, and possess a broad transition temperature. The recovery of multiple temporary shapes of electrospun membranes can be triggered by heat in a single triple-, quadruple-, quintuple-shape memory cycle, respectively. The fiber morphology and nanometer size provide unprecedented design flexibility for the adjustable morphing effect. SMFMs enable complex deformations at need, having a wide potential application field including smart textiles, artificial intelligence robots, bio-medical engineering, aerospace technologies, etc in the future.

Electro-Optic Properties of Holographically Patterned, Polymer Stabilized Cholesteric Liquid Crystals (Preprint)

DTIC Science & Technology

2007-01-01

Electro - optic properties of cholesteric liquid crystals with holographically patterned polymer stabilization were examined. It is hypothesized that...enhanced electro - optic properties of the final device. Prior to holographic patterning, polymer stabilization with large elastic memory was generated by way... electro - optic properties appear to stem from a single dimension domain size increase, which allows for a reduction in the LC/polymer interaction.

Influence of Thin-Film Adhesives in Pullout Tests Between Nickel-Titanium Shape Memory Alloy and Carbon Fiber-Reinforced Polymer Matrix Composites

NASA Technical Reports Server (NTRS)

Quade, Derek J.; Jana, Sadhan; McCorkle, Linda S.

2018-01-01

Strips of nickel-titanium (NiTi) shape memory alloy (SMA) and carbon fiber-reinforced polymer matrix composite (PMC) were bonded together using multiple thin film adhesives and their mechanical strengths were evaluated under pullout test configuration. Tensile and lap shear tests were conducted to confirm the deformation of SMAs at room temperature and to evaluate the adhesive strength between the NiTi strips and the PMC. Optical and scanning electron microscopy techniques were used to examine the interfacial bonding after failure. Simple equations on composite tensile elongation were used to fit the experimental data on tensile properties. ABAQUS models were generated to show the effects of enhanced bond strength and the distribution of stress in SMA and PMC. The results revealed that the addition of thin film adhesives increased the average adhesive strength between SMA and PMC while halting the room temperature shape memory effect within the pullout specimen.

Redox driven conductance changes for resistive memory

NASA Astrophysics Data System (ADS)

Shoute, Lian C. T.; Pekas, Nikola; Wu, Yiliang; McCreery, Richard L.

2011-03-01

The relationship between bias-induced redox reactions and resistance switching is considered for memory devices containing TiO2 or a conducting polymer in "molecular heterojunctions" consisting of thin (2-25 nm) films of covalently bonded molecules, polymers, and oxides. Raman spectroscopy was used to monitor changes in the oxidation state of polythiophene in Au/P3HT/SiO2/Au devices, and it was possible to directly determine the formation and stability of the conducting polaron state of P3HT by applied bias pulses [P3HT = poly(3-hexyl thiophene)]. Polaron formation was strongly dependent on junction composition, particularly on the interfaces between the polymer, oxide, and electrodes. In all cases, trace water was required for polaron formation, leading to the proposal that water reduction acts as a redox counter-reaction to polymer oxidation. Polaron stability was longest for the case of a direct contact between Au and SiO2, implying that catalytic water reduction at the Au surface generated hydroxide ions which stabilized the cationic polaron. The spectroscopic information about the dependence of polaron stability on device composition will be useful for designing and monitoring resistive switching memory based on conducting polymers, with or without TiO2 present.

Development of high shrinkage polyethylene terephthalate (PET) shape memory polymer tendons for concrete crack closure

NASA Astrophysics Data System (ADS)

Teall, Oliver; Pilegis, Martins; Sweeney, John; Gough, Tim; Thompson, Glen; Jefferson, Anthony; Lark, Robert; Gardner, Diane

2017-04-01

The shrinkage force exerted by restrained shape memory polymers (SMPs) can potentially be used to close cracks in structural concrete. This paper describes the physical processing and experimental work undertaken to develop high shrinkage die-drawn polyethylene terephthalate (PET) SMP tendons for use within a crack closure system. The extrusion and die-drawing procedure used to manufacture a series of PET tendon samples is described. The results from a set of restrained shrinkage tests, undertaken at differing activation temperatures, are also presented along with the mechanical properties of the most promising samples. The stress developed within the tendons is found to be related to the activation temperature, the cross-sectional area and to the draw rate used during manufacture. Comparisons with commercially-available PET strip samples used in previous research are made, demonstrating an increase in restrained shrinkage stress by a factor of two for manufactured PET filament samples.

A preliminary study on shape recovery speed of a styrene-based shape memory polymer composite actuated by different heating methods

NASA Astrophysics Data System (ADS)

Wu, Xuelian; Zhang, Wuyi; Liu, Yanju; Leng, Jinsong

2007-07-01

Thermally activated shape memory polymers (SMPs) receive increasing attention in recent years. Different from those reported in the literature, in this paper we propose a new approach, i.e., using infrared light, for heating SMPs for shape recovery. We compare this approach with the traditional water bath method in terms of shape recovery speed in bending at both vacuum and no vacuum conditions. The results reveal that the shape recovery speed in infrared heating at vacuum condition is about eight times slower than that by hot water. However, the recovery time is more than doubled if without vacuum.

Folate receptor‐targeted aminoglycoside‐derived polymers for transgene expression in cancer cells

PubMed Central

Godeshala, Sudhakar; Nitiyanandan, Rajeshwar; Thompson, Brian; Goklany, Sheba; Nielsen, David R.

2016-01-01

Abstract Targeted delivery of anticancer therapeutics can potentially overcome the limitations associated with current chemotherapeutic regimens. Folate receptors are overexpressed in several cancers, including ovarian, triple‐negative breast and bladder cancers, making them attractive for targeted delivery of nucleic acid therapeutics to these tumors. This work describes the synthesis, characterization and evaluation of folic acid‐conjugated, aminoglycoside‐derived polymers for targeted delivery of transgenes to breast and bladder cancer cell lines. Transgene expression was significantly higher with FA‐conjugated aminoglycoside‐derived polymers than with Lipofectamine, and these polymers demonstrated minimal cytotoxicty. Competitive inhibition using free folic acid significantly reduced transgene expression efficacy of folate‐targeted polymers, suggesting a role for folate receptor‐mediated uptake. High efficacy FA‐targeted polymers were employed to deliver a plasmid expressing the TRAIL protein, which induced death in cancer cells. These results indicate that FA‐conjugated aminoglycoside‐derived polymers are promising for targeted delivery of nucleic acids to cancer cells that overexpress folate receptors. PMID:29313013

Frequency-dependent learning achieved using semiconducting polymer/electrolyte composite cells

NASA Astrophysics Data System (ADS)

Dong, W. S.; Zeng, F.; Lu, S. H.; Liu, A.; Li, X. J.; Pan, F.

2015-10-01

Frequency-dependent learning has been achieved using semiconducting polymer/electrolyte composite cells. The cells composed of polymer/electrolyte double layers realized the conventional spike-rate-dependent plasticity (SRDP) learning model. These cells responded to depression upon low-frequency stimulation and to potentiation upon high-frequency stimulation and presented long-term memory. The transition threshold θm from depression to potentiation varied depending on the previous stimulations. A nanostructure resembling a bio-synapse in its transport passages was demonstrated and a random channel model was proposed to describe the ionic kinetics at the polymer/electrolyte interface during and after stimulations with various frequencies, accounting for the observed SRDP.Frequency-dependent learning has been achieved using semiconducting polymer/electrolyte composite cells. The cells composed of polymer/electrolyte double layers realized the conventional spike-rate-dependent plasticity (SRDP) learning model. These cells responded to depression upon low-frequency stimulation and to potentiation upon high-frequency stimulation and presented long-term memory. The transition threshold θm from depression to potentiation varied depending on the previous stimulations. A nanostructure resembling a bio-synapse in its transport passages was demonstrated and a random channel model was proposed to describe the ionic kinetics at the polymer/electrolyte interface during and after stimulations with various frequencies, accounting for the observed SRDP. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02891d

An electrical-heating and self-sensing shape memory polymer composite incorporated with carbon fiber felt

NASA Astrophysics Data System (ADS)

Gong, Xiaobo; Liu, Liwu; Liu, Yanju; Leng, Jinsong

2016-03-01

Shape memory polymers (SMPs) have the ability to adjust their stiffness, lock a temporary shape, and recover the permanent shape upon imposing an appropriate stimulus. They have found their way into the field of morphing structures. The electrically Joule resistive heating of the conductive composite can be a desirable stimulus to activate the shape memory effect of SMPs without external heating equipment. Electro-induced SMP composites incorporated with carbon fiber felt (CFF) were explored in this work. The CFF is an excellent conductive filler which can easily spread throughout the composite. It has a huge advantage in terms of low cost, simple manufacturing process, and uniform and tunable temperature distribution while heating. A continuous and compact conductive network made of carbon fibers and the overlap joints among them was observed from the microscopy images, and this network contributes to the high conductive properties of the CFF/SMP composites. The CFF/SMP composites can be electrical-heated rapidly and uniformly, and its’ shape recovery effect can be actuated by the electrical resistance Joule heating of the CFF without an external heater. The CFF/SMP composite get higher modulus and higher strength than the pure SMP without losing any strain recovery property. The high dependence of temperature and strain on the electrical resistance also make the composite a good self-sensing material. In general, the CFF/SMP composite shows great prospects as a potential material for the future morphing structures.

Polymer chemistry: Proteins in a pill

NASA Astrophysics Data System (ADS)

Maynard, Heather D.

2013-07-01

Protein drugs are important therapies for many different diseases, but very few can be administered orally. Now, a cationic dendronized polymer has been shown to stabilize a therapeutic protein for delivery to the gut.

Modeling the behaviour of shape memory materials under large deformations

NASA Astrophysics Data System (ADS)

Rogovoy, A. A.; Stolbova, O. S.

2017-06-01

In this study, the models describing the behavior of shape memory alloys, ferromagnetic materials and polymers have been constructed, using a formalized approach to develop the constitutive equations for complex media under large deformations. The kinematic and constitutive equations, satisfying the principles of thermodynamics and objectivity, have been derived. The application of the Galerkin procedure to the systems of equations of solid mechanics allowed us to obtain the Lagrange variational equation and variational formulation of the magnetostatics problems. These relations have been tested in the context of the problems of finite deformation in shape memory alloys and ferromagnetic materials during forward and reverse martensitic transformations and in shape memory polymers during forward and reverse relaxation transitions from a highly elastic to a glassy state.

Shape Memory Polymers Containing Higher Acrylate Content Display Increased Endothelial Cell Attachment

PubMed Central

Govindarajan, Tina; Shandas, Robin

2018-01-01

Shape Memory Polymers (SMPs) are smart materials that can recall their shape upon the application of a stimulus, which makes them appealing materials for a variety of applications, especially in biomedical devices. Most prior SMP research has focused on tuning bulk properties; studying surface effects of SMPs may extend the use of these materials to blood-contacting applications, such as cardiovascular stents, where surfaces that support rapid endothelialization have been correlated to stent success. Here, we evaluate endothelial attachment onto the surfaces of a family of SMPs previously developed in our group that have shown promise for biomedical devices. Nine SMP formulations containing varying amounts of tert-Butyl acrylate (tBA) and Poly(ethylene glycol) dimethacrylate (PEGDMA) were analyzed for endothelial cell attachment. Dynamic mechanical analysis (DMA), contact angle studies, and atomic force microscopy (AFM) were used to verify bulk and surface properties of the SMPs. Human umbilical vein endothelial cell (HUVEC) attachment and viability was verified using fluorescent methods. Endothelial cells preferentially attached to SMPs with higher tBA content, which have rougher, more hydrophobic surfaces. HUVECs also displayed an increased metabolic activity on these high tBA SMPs over the course of the study. This class of SMPs may be promising candidates for next generation blood-contacting devices. PMID:29707382

Nanoporous capsules of block co-polymers of [(MeO-PEG-NH)-b-(L-GluA)]-PCL for the controlled release of anticancer drugs for therapeutic applications.

PubMed

Amgoth, Chander; Dharmapuri, Gangappa; Kalle, Arunasree M; Paik, Pradip

2016-03-29

Herein, new nanoporous capsules of the block co-polymers of MeO-PEG-NH-(L-GluA)10 and polycaprolactone (PCL) have been synthesized through a surfactant-free cost-effective self-assembled soft-templating approach for the controlled release of drugs and for therapeutic applications. The nanoporous polymer capsules are designed to be biocompatible and are capable of encapsulating anticancer drugs (e.g., doxorubicin hydrochloride (DOX) and imatinib mesylate (ITM)) with a high extent (∼279 and ∼480 ng μg(-1), respectively). We have developed a nanoformulation of porous MeO-PEG-NH-(L-GluA)10-PCL capsules with DOX and ITM. The porous polymer nanoformulations have been programmed in terms of the release of anticancer drugs with a desired dose to treat the leukemia (K562) and human carcinoma cells (HepG2) in vitro and show promising IC50 values with a very high mortality of cancer cells (up to ∼96.6%). Our nanoformulation arrests the cell divisions due to 'cellular scenescence' and kills the cancer cells specifically. The present findings could enrich the effectiveness of idiosyncratic nanoporous polymer capsules for use in various other nanomedicinal and biomedical applications, such as for killing cancer cells, immune therapy, and gene delivery.

Nanoporous capsules of block co-polymers of [(MeO-PEG-NH)-b-(L-GluA)]-PCL for the controlled release of anticancer drugs for therapeutic applications

NASA Astrophysics Data System (ADS)

Amgoth, Chander; Dharmapuri, Gangappa; Kalle, Arunasree M.; Paik, Pradip

2016-03-01

Herein, new nanoporous capsules of the block co-polymers of MeO-PEG-NH-(L-GluA)10 and polycaprolactone (PCL) have been synthesized through a surfactant-free cost-effective self-assembled soft-templating approach for the controlled release of drugs and for therapeutic applications. The nanoporous polymer capsules are designed to be biocompatible and are capable of encapsulating anticancer drugs (e.g., doxorubicin hydrochloride (DOX) and imatinib mesylate (ITM)) with a high extent (˜279 and ˜480 ng μg-1, respectively). We have developed a nanoformulation of porous MeO-PEG-NH-(L-GluA)10-PCL capsules with DOX and ITM. The porous polymer nanoformulations have been programmed in terms of the release of anticancer drugs with a desired dose to treat the leukemia (K562) and human carcinoma cells (HepG2) in vitro and show promising IC50 values with a very high mortality of cancer cells (up to ˜96.6%). Our nanoformulation arrests the cell divisions due to ‘cellular scenescence’ and kills the cancer cells specifically. The present findings could enrich the effectiveness of idiosyncratic nanoporous polymer capsules for use in various other nanomedicinal and biomedical applications, such as for killing cancer cells, immune therapy, and gene delivery.

The power of living things: Living memorials as therapeutic landscapes

Treesearch

Heather L. McMillen; Lindsay K. Campbell; Erika S. Svendsen

2017-01-01

In response to the events of 11 September 2001 (9/11), many communities came together to create living memorials. Many living memorials were established near the crash sites, but others were created across the United States from urban to rural areas, with designs ranging from entire forests to single trees. They were created by surviving family members, supporters of...

In vitro and in vivo Evaluation of a Shape Memory Polymer Foam-over-Wire Embolization Device Delivered in Saccular Aneurysm Models

PubMed Central

Boyle, Anthony J.; Landsman, Todd L.; Wierzbicki, Mark A.; Nash, Landon D.; Hwang, Wonjun; Miller, Matthew W.; Tuzun, Egemen; Hasan, Sayyeda M.; Maitland, Duncan J.

2015-01-01

Current endovascular therapies for intracranial saccular aneurysms result in high recurrence rates due to poor tissue healing, coil compaction, and aneurysm growth. We propose treatment of saccular aneurysms using shape memory polymer (SMP) foam to improve clinical outcomes. SMP foam-over-wire (FOW) embolization devices were delivered to in vitro and in vivo porcine saccular aneurysm models to evaluate device efficacy, aneurysm occlusion, and acute clotting. FOW devices demonstrated effective delivery and stable implantation in vitro. In vivo porcine aneurysms were successfully occluded using FOW devices with theoretical volume occlusion values greater than 72% and rapid, stable thrombus formation. PMID:26227115

Shape forming by thermal expansion mismatch and shape memory locking in polymer/elastomer laminates

NASA Astrophysics Data System (ADS)

Yuan, Chao; Ding, Zhen; Wang, T. J.; Dunn, Martin L.; Qi, H. Jerry

2017-10-01

This paper studies a novel method to fabricate three-dimensional (3D) structure from 2D thermo-responsive shape memory polymer (SMP)/elastomer bilayer laminate. In this method, the shape change is actuated by the thermal mismatch strain between the SMP and the elastomer layers upon heating. However, the glass transition behavior of the SMP locks the material into a new 3D shape that is stable even upon cooling. Therefore, the second shape becomes a new permanent shape of the laminate. A theoretical model that accounts for the temperature-dependent thermomechanical behavior of the SMP material and thermal mismatch strain between the two layers is developed to better understand the underlying physics. Model predictions and experiments show good agreement and indicate that the theoretical model can well predict the bending behavior of the bilayer laminate. The model is then used in the optimal design of geometrical configuration and material selection. The latter also illustrates the requirement of thermomechanical behaviors of the SMP to lock the shape. Based on the fundamental understandings, several self-folding structures are demonstrated by the bilayer laminate design.

Modelling of loading, stress relaxation and stress recovery in a shape memory polymer.

PubMed

Sweeney, J; Bonner, M; Ward, I M

2014-09-01

A multi-element constitutive model for a lactide-based shape memory polymer has been developed that represents loading to large tensile deformations, stress relaxation and stress recovery at 60, 65 and 70°C. The model consists of parallel Maxwell arms each comprising neo-Hookean and Eyring elements. Guiu-Pratt analysis of the stress relaxation curves yields Eyring parameters. When these parameters are used to define the Eyring process in a single Maxwell arm, the resulting model yields at too low a stress, but gives good predictions for longer times. Stress dip tests show a very stiff response on unloading by a small strain decrement. This would create an unrealistically high stress on loading to large strain if it were modelled by an elastic element. Instead it is modelled by an Eyring process operating via a flow rule that introduces strain hardening after yield. When this process is incorporated into a second parallel Maxwell arm, there results a model that fully represents both stress relaxation and stress dip tests at 60°C. At higher temperatures a third arm is required for valid predictions. Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.

Drug-Free Macromolecular Therapeutics – A New Paradigm in Polymeric Nanomedicines

PubMed Central

Chu, Te-Wei; Kopeček, Jindřich

2015-01-01

This review highlights a unique research area in polymer-based nanomedicine designs. Drug-free macromolecular therapeutics induce apoptosis of malignant cells by the crosslinking of surface non-internalizing receptors. The receptor crosslinking is mediated by the biorecognition of high-fidelity natural binding motifs (such as antiparallel coiled-coil peptides or complementary oligonucleotides) that are grafted to the side chains of polymers or attached to targeting moieties against cell receptors. This approach features the absence of low-molecular-weight cytotoxic compounds. Here, we summarize the rationales, different designs, and advantages of drug-free macromolecular therapeutics. Recent developments of novel therapeutic systems for B-cell lymphomas are discussed, as well as relevant approaches for other diseases. We conclude by pointing out various potential future directions in this exciting new field. PMID:26191406

Supramolecular Polymer Nanocomposites - Improvement of Mechanical Properties

NASA Astrophysics Data System (ADS)

Hinricher, Jesse; Neikirk, Colin; Priestley, Rodney

2015-03-01

Supramolecular polymers differ from traditional polymers in that their repeat units are connected by hydrogen bonds that can reversibly break and form under various stimuli. They can be more easily recycled than conventional materials, and their highly temperature dependent viscosities result in reduced energy consumption and processing costs. Furthermore, judicious selection of supramolecular polymer architecture and functionality allows the design of advanced materials including shape memory and self-healing materials. Supramolecular polymers have yet to see widespread use because they can't support much weight due to their inherent mechanical weakness. In order to address this issue, the mechanical strength of supramolecular polymer nanocomposites based on ureidopyrmidinone (UPy) telechelic poly(caprolactone) doped with surface activated silica nanoparticles was investigated by tensile testing and dynamic mechanical analysis. The effects of varying amounts and types of nanofiller surface functionality were investigated to glean insight into the contributions of filler-filler and filler-matrix interactions to mechanical reinforcement in supramolecular polymer nanocomposites. MRSEC NSF DMR 0819860 (PI: Prof. N. Phuan Ong) REU Site Grant: NSF DMR-1156422 (PI: Prof. Mikko Haataja)

A Very Simple Strategy for Preparing External Stress-Free Two-Way Shape Memory Polymers by Making Use of Hydrogen Bonds.

PubMed

Fan, Long Fei; Rong, Min Zhi; Zhang, Ming Qiu; Chen, Xu Dong

2018-05-11

Development of two-way shape memory polymers that operate free of external force remains a great challenge. Here, the design criteria for this type of material are proposed, deriving a novel fabrication strategy accordingly, which employs conventional crosslinked polyurethane (PU) containing crystalline poly(ε-caprolactone) (PCL) as the proof-of-concept material. Having been simply trained by stretching and thermal treatment without additional ingredients and chemicals, the PU is coupled with a two-way shape memory effect. The core advancement of this study lies in the successful conversion of the inherent hydrogen bond network, which is often the easiest to overlook, into an internal stress provider. The temperature-dependent reversible melting/recrystallization of the crystalline phases elaborately works with the tensed hydrogen bond network, leading to implementation of the two-way shape memory effect. An average reversible strain of as high as ≈20% along the stretch direction is obtained through cooperation adjustment of chemical crosslinking density, crystallinity, and concentration of hydrogen bonds. Meanwhile, the highest internal tension offered by the hydrogen bond network is determined to be 0.10 MPa. Owing to the great convenience characterized by material selection, preparation, programming, and application, the current work may open up an avenue for production and usage of the smart material. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymers in Small-Interfering RNA Delivery

PubMed Central

Singha, Kaushik; Namgung, Ran

2011-01-01

This review will cover the current strategies that are being adopted to efficiently deliver small interfering RNA using nonviral vectors, including the use of polymers such as polyethylenimine, poly(lactic-co-glycolic acid), polypeptides, chitosan, cyclodextrin, dendrimers, and polymers-containing different nanoparticles. The article will provide a brief and concise account of underlying principle of these polymeric vectors and their structural and functional modifications which were intended to serve different purposes to affect efficient therapeutic outcome of small-interfering RNA delivery. The modifications of these polymeric vectors will be discussed with reference to stimuli-responsiveness, target specific delivery, and incorporation of nanoconstructs such as carbon nanotubes, gold nanoparticles, and silica nanoparticles. The emergence of small-interfering RNA as the potential therapeutic agent and its mode of action will also be mentioned in a nutshell. PMID:21749290

Thermomechanical behavior of shape memory elastomeric composites

NASA Astrophysics Data System (ADS)

Ge, Qi; Luo, Xiaofan; Rodriguez, Erika D.; Zhang, Xiao; Mather, Patrick T.; Dunn, Martin L.; Qi, H. Jerry

2012-01-01

Shape memory polymers (SMPs) can fix a temporary shape and recover their permanent shape in response to environmental stimuli such as heat, electricity, or irradiation. Most thermally activated SMPs use the macromolecular chain mobility change around the glass transition temperature ( Tg) to achieve the shape memory (SM) effects. During this process, the stiffness of the material typically changes by three orders of magnitude. Recently, a composite materials approach was developed to achieve thermally activated shape memory effect where the material exhibits elastomeric response in both the temporary and the recovered configurations. These shape memory elastomeric composites (SMECs) consist of an elastomeric matrix reinforced by a semicrystalline polymer fiber network. The matrix provides background rubber elasticity while the fiber network can transform between solid crystals and melt phases over the operative temperature range. As such it serves as a reversible "switching phase" that enables shape fixing and recovery. Shape memory elastomeric composites provide a new paradigm for the development of a wide array of active polymer composites that utilize the melt-crystal transition to achieve the shape memory effect. This potentially allows for material systems with much simpler chemistries than most shape memory polymers and thus can facilitate more rapid material development and insertion. It is therefore important to understand the thermomechanical behavior and to develop corresponding material models. In this paper, a 3D finite-deformation constitutive modeling framework was developed to describe the thermomechanical behavior of SMEC. The model is phenomenological, although inspired by micromechanical considerations of load transfer between the matrix and fiber phases of a composite system. It treats the matrix as an elastomer and the fibers as a complex solid that itself is an aggregate of melt and crystal phases that evolve from one to the other during a

Biomedical applications of polymers derived by reversible addition - fragmentation chain-transfer (RAFT).

PubMed

Fairbanks, Benjamin D; Gunatillake, Pathiraja A; Meagher, Laurence

2015-08-30

RAFT- mediated polymerization, providing control over polymer length and architecture as well as facilitating post polymerization modification of end groups, has been applied to virtually every facet of biomedical materials research. RAFT polymers have seen particularly extensive use in drug delivery research. Facile generation of functional and telechelic polymers permits straightforward conjugation to many therapeutic compounds while synthesis of amphiphilic block copolymers via RAFT allows for the generation of self-assembled structures capable of carrying therapeutic payloads. With the large and growing body of literature employing RAFT polymers as drug delivery aids and vehicles, concern over the potential toxicity of RAFT derived polymers has been raised. While literature exploring this complication is relatively limited, the emerging consensus may be summed up in three parts: toxicity of polymers generated with dithiobenzoate RAFT agents is observed at high concentrations but not with polymers generated with trithiocarbonate RAFT agents; even for polymers generated with dithiobenzoate RAFT agents, most reported applications call for concentrations well below the toxicity threshold; and RAFT end-groups may be easily removed via any of a variety of techniques that leave the polymer with no intrinsic toxicity attributable to the mechanism of polymerization. The low toxicity of RAFT-derived polymers and the ability to remove end groups via straightforward and scalable processes make RAFT technology a valuable tool for practically any application in which a polymer of defined molecular weight and architecture is desired. Copyright © 2015. Published by Elsevier B.V.

Polymer-induced compression of biological hydrogels

NASA Astrophysics Data System (ADS)

Datta, Sujit; Preska Steinberg, Asher; Ismagilov, Rustem

Hydrogels - such as mucus, blood clots, and the extracellular matrix - provide critical functions in biological systems. However, little is known about how their structure is influenced by many of the polymeric materials they come into contact with regularly. Here, we focus on one critically important biological hydrogel: colonic mucus. While several biological processes are thought to potentially regulate the mucus hydrogel structure, the polymeric composition of the gut environment has been ignored. We use Flory-Huggins solution theory to characterize polymer-mucus interactions. We find that gut polymers, including those small enough to penetrate the mucus hydrogel, can in fact alter mucus structure, changing its equilibrium degree of swelling and forcing it to compress. The extent of compression increases with increasing polymer concentration and size. We use experiments on mice to verify these predictions with common dietary and therapeutic gut polymers. Our results provide a foundation for investigating similar, previously overlooked, polymer-induced effects in other biological hydrogels.

Understanding Melt-Memory of Commercial Polyolefins

NASA Astrophysics Data System (ADS)

Alamo, Rufina

Self-nucleation (SN) or controlling self-generated seeds in a polymer melt is an avenue to increase the rate of solidification of semicrystalline polymers of commercial relevance. Self-nuclei are remains in the melt of the segmental self-assembly to form polymer crystallites providing a path to enhance primary crystal nucleation. SN has been extensively studied in homopolymers such as iPP. Recently, a strong memory effect of crystallization has been observed in melts of random ethylene copolymers well above the equilibrium melting temperature. The melt memory is associated with clusters or seeds that remain in the melt from the copolymer's sequence length partitioning. Cooling from progressively lower self-seeded melt temperatures, ethylene copolymers with a broad inter-chain comonomer composition (1 - 15 mol%) display first the expected accelerated crystallization, followed by a decrease in the rate in a range of melt temperatures where narrow copolymers show a continuous acceleration of the rate. This unusual inversion of the crystallization rate was postulated to arise from the onset of liquid-liquid phase separation (LLPS) between comonomer-rich and comonomer-poor components of the broad copolymer. The UCST type phase diagram of these commercial copolymers has been documented via SANS using a blend of components, some deuterated, to reproduce the broad distribution. Furthermore, the components that contribute to LLPS have been identified by the crystallization behavior of molar mass fractions. The influence of long chain branching on the topology of copolymer melts has been analyzed using model 3-arm stars hydrogenated polybutadienes. The effect of melt viscosity on strength of melt memory is also evident when SN data of random ethylene copolymers are compared with those of propylene-ethylene copolymers. The strong dependence of melt viscosity on melt memory, and a critical threshold crystallinity level to observe the effect of melt memory on crystallization

Optical polymers for laser medical applications

NASA Astrophysics Data System (ADS)

Sultanova, Nina G.; Kasarova, Stefka N.; Nikolov, Ivan D.

2016-01-01

In medicine, optical polymers are used not only in ophthalmology but in many laser surgical, diagnostic and therapeutic systems. The application in lens design is determined by their refractive and dispersive properties in the considered spectral region. We have used different measuring techniques to obtain precise refractometric data in the visible and near-infrared spectral regions. Dispersive, thermal and other important optical characteristics of polymers have been studied. Design of a plastic achromatic objective, used in a surgical stereo-microscope at 1064 nm laser wavelength, is accomplished. Geometrical and wavefront aberrations are calculated. Another example of application of polymers is the designed all-mirror apochromatic micro-lens, intended for superluminescent diode fiber coupling in medical systems.

Memory reconsolidation, emotional arousal, and the process of change in psychotherapy: New insights from brain science.

PubMed

Lane, Richard D; Ryan, Lee; Nadel, Lynn; Greenberg, Leslie

2015-01-01

Since Freud, clinicians have understood that disturbing memories contribute to psychopathology and that new emotional experiences contribute to therapeutic change. Yet, controversy remains about what is truly essential to bring about psychotherapeutic change. Mounting evidence from empirical studies suggests that emotional arousal is a key ingredient in therapeutic change in many modalities. In addition, memory seems to play an important role but there is a lack of consensus on the role of understanding what happened in the past in bringing about therapeutic change. The core idea of this paper is that therapeutic change in a variety of modalities, including behavioral therapy, cognitive-behavioral therapy, emotion-focused therapy, and psychodynamic psychotherapy, results from the updating of prior emotional memories through a process of reconsolidation that incorporates new emotional experiences. We present an integrated memory model with three interactive components - autobiographical (event) memories, semantic structures, and emotional responses - supported by emerging evidence from cognitive neuroscience on implicit and explicit emotion, implicit and explicit memory, emotion-memory interactions, memory reconsolidation, and the relationship between autobiographical and semantic memory. We propose that the essential ingredients of therapeutic change include: (1) reactivating old memories; (2) engaging in new emotional experiences that are incorporated into these reactivated memories via the process of reconsolidation; and (3) reinforcing the integrated memory structure by practicing a new way of behaving and experiencing the world in a variety of contexts. The implications of this new, neurobiologically grounded synthesis for research, clinical practice, and teaching are discussed.

3D Printed Silicones with Shape Memory

DOE PAGES

Wu, Amanda S.; Small IV, Ward; Bryson, Taylor M.; ...

2017-07-05

Direct ink writing enables the layer-by-layer manufacture of ordered, porous structures whose mechanical behavior is driven by architecture and material properties. Here, we incorporate two different gas filled microsphere pore formers to evaluate the effect of shell stiffness and T g on compressive behavior and compression set in siloxane matrix printed structures. The lower T g microsphere structures exhibit substantial compression set when heated near and above T g, with full structural recovery upon reheating without constraint. By contrast, the higher T g microsphere structures exhibit reduced compression set with no recovery upon reheating. Aside from their role in tuningmore » the mechanical behavior of direct ink write structures, polymer microspheres are good candidates for shape memory elastomers requiring structural complexity, with potential applications toward tandem shape memory polymers.« less

3D Printed Silicones with Shape Memory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Amanda S.; Small IV, Ward; Bryson, Taylor M.

Direct ink writing enables the layer-by-layer manufacture of ordered, porous structures whose mechanical behavior is driven by architecture and material properties. Here, we incorporate two different gas filled microsphere pore formers to evaluate the effect of shell stiffness and T g on compressive behavior and compression set in siloxane matrix printed structures. The lower T g microsphere structures exhibit substantial compression set when heated near and above T g, with full structural recovery upon reheating without constraint. By contrast, the higher T g microsphere structures exhibit reduced compression set with no recovery upon reheating. Aside from their role in tuningmore » the mechanical behavior of direct ink write structures, polymer microspheres are good candidates for shape memory elastomers requiring structural complexity, with potential applications toward tandem shape memory polymers.« less

Transition state analogue imprinted polymers as artificial amidases for amino acid p-nitroanilides: morphological effects of polymer network on catalytic efficiency.

PubMed

Mathew, Divya; Thomas, Benny; Devaky, K S

2017-11-13

The morphology of the polymer network - porous/less porous - plays predominant role in the amidase activities of the polymer catalysts in the hydrolytic reactions of amino acid p-nitroanilides. Polymers with the imprints of stable phosphonate analogue of the intermediate of hydrolytic reactions were synthesized as enzyme mimics. Molecular imprinting was carried out in thermodynamically stable porogen dimethyl sulphoxide and unstable porogen chloroform, to investigate the morphological effects of polymers on catalytic amidolysis. It was found that the medium of polymerization has vital influence in the amidase activities of the enzyme mimics. The morphological studies of the polymer catalysts were carried out by scanning electron microscopy and Bruner-Emmett-Teller analysis. The morphology of the polymer catalysts and their amidase activities are found to be dependent on the composition of reaction medium. The polymer catalyst prepared in dimethyl sulphoxide is observed to be efficient in 1:9 acetonitrile (ACN)-Tris HCl buffer and that prepared in chloroform is noticed to be stereo specifically and shape-selectively effective in 9:1 ACN-Tris HCl buffer. The solvent memory effect in catalytic amidolysis was investigated using the polymer prepared in acetonitrile.

Implementation of poly(ε-caprolactone) sheet-based shape-memory polymer microvalves into plastic-based microfluidic devices

NASA Astrophysics Data System (ADS)

Jiang, Chenyang; Uto, Koichiro; Ebara, Mitsuhiro; Aoyagi, Takao; Ichiki, Takanori

2015-06-01

Implementation of shape-memory polymer (SMP) sheet-based microvalves into plastic-based microfluidic devices has been studied toward the use in disposable and mass producible micro total analysis devices. Poly(ε-caprolactone) (PCL) and poly(methyl methacrylate-co-styrene) (MS) were used as SMP and main substrate materials, respectively. Bonding between PCL sheets and MS plates was the critical issue in the practical implementation. We found the pristine PCL sheet has relatively rough surface with Ra of 85.14 nm, which is the cause of poor bonding. Hence, by introducing the post-anneal treatment with sandwiched between two flat glass plates, the PCL surface could be smoothed to Ra of 12.50 nm, and tight bonding could be obtained. Consequently, microfluidic devices consisting of plastic/PCL/plastic layers were successfully fabricated and therein the actuation of SMP valves without any leakage was demonstrated. The present technology is expected to be applicable to disposable microfluidic devices as required for point-of-care testing.

Computational Modeling of Shape Memory Polymer Origami that Responds to Light

NASA Astrophysics Data System (ADS)

Mailen, Russell William

Shape memory polymers (SMPs) transform in response to external stimuli, such as infrared (IR) light. Although SMPs have many applications, this investigation focuses on their use as actuators in self-folding origami structures. Ink patterned on the surface of the SMP sheet absorbs thermal energy from the IR light, which produces localized heating. The material shrinks wherever the activation temperature is exceeded and can produce out-of-plane deformation. The time and temperature dependent response of these SMPs provides unique opportunities for developing complex three-dimensional (3D) structures from initially flat sheets through self-folding origami, but the application of this technique requires predicting accurately the final folded or deformed shape. Furthermore, current computational approaches for SMPs do not fully couple the thermo-mechanical response of the material. Hence, a proposed nonlinear, 3D, thermo-viscoelastic finite element framework was formulated to predict deformed shapes for different self-folding systems and compared to experimental results for self-folding origami structures. A detailed understanding of the shape memory response and the effect of controllable design parameters, such as the ink pattern, pre-strain conditions, and applied thermal and mechanical fields, allows for a predictive understanding and design of functional, 3D structures. The proposed modeling framework was used to obtain a fundamental understanding of the thermo-mechanical behavior of SMPs and the impact of the material behavior on hinged self-folding. These predictions indicated how the thermal and mechanical conditions during pre-strain significantly affect the shrinking and folding response of the SMP. Additionally, the externally applied thermal loads significantly influenced the folding rate and maximum bending angle. The computational framework was also adapted to understand the effects of fully coupling the thermal and mechanical response of the material

A ‘frozen volume’ transition model and working mechanism for the shape memory effect in amorphous polymers

NASA Astrophysics Data System (ADS)

Lu, Haibao; Wang, Xiaodong; Yao, Yongtao; Qing Fu, Yong

2018-06-01

Phenomenological models based on frozen volume parameters could well predict shape recovery behavior of shape memory polymers (SMPs), but the physical meaning of using the frozen volume parameters to describe thermomechanical properties has not been well-established. In this study, the fundamental working mechanisms of the shape memory effect (SME) in amorphous SMPs, whose temperature-dependent viscoelastic behavior follows the Eyring equation, have been established with the considerations of both internal stress and its resulted frozen volume. The stress-strain constitutive relation was initially modeled to quantitatively describe effects of internal stresses at the macromolecular scale based on the transient network theory. A phenomenological ‘frozen volume’ model was then established to characterize the macromolecule structure and SME of amorphous SMPs based on a two-site stress-relaxation model. Effects of the internal stress, frozen volume and strain rate on shape memory behavior and thermomechanical properties of the SMP were investigated. Finally, the simulation results were compared with the experimental results reported in the literature, and good agreements between the theoretical and experimental results were achieved. The novelty and key differences of our newly proposed model with respect to the previous reports are (1). The ‘frozen volume’ in our study is caused by the internal stress and governed by the two-site model theory, thus has a good physical meaning. (2). The model can be applied to characterize and predict both the thermal and thermomechanical behaviors of SMPs based on the constitutive relationship with internal stress parameters. It is expected to provide a power tool to investigate the thermomechanical behavior of the SMPs, of which both the macromolecular structure characteristics and SME could be predicted using this ‘frozen volume’ model.

Fabrication of nylon/fullerene polymer memory

NASA Astrophysics Data System (ADS)

Jayan, Manuvel; Davis, Rosemary; Karthik, M. P.; Devika, K.; Kumar, G. Vijay; Sriraj, B.; Predeep, P.

2017-06-01

Two terminal Organic memories in passive matrix array form with device structure, Al/Nylon/ (Nylon+C60)/Nylon/ Al are fabricated. The current-voltage measurements showed hysteresis and the devices are thoroughly characterized for write-read-erase-read cycles. The control over the dispersion concentration, capacity of fullerene to readily accept electrons and the constant diameter of fullerene made possible uniform device fabrication with reproducible results. Scanning electron micrographs indicated that the device thickness remained uniform in the range of 19 micrometers.

Main chain acid-degradable polymers for the delivery of bioactive materials

DOEpatents

Frechet, Jean M. J. [Oakland, CA; Standley, Stephany M [Evanston, IL; Jain, Rachna [Milpitas, CA; Lee, Cameron C [Cambridge, MA

2012-03-20

Novel main chain acid degradable polymer backbones and drug delivery systems comprised of materials capable of delivering bioactive materials to cells for use as vaccines or other therapeutic agents are described. The polymers are synthesized using monomers that contain acid-degradable linkages cleavable under mild acidic conditions. The main chain of the resulting polymers readily degrade into many small molecules at low pH, but remain relatively stable and intact at physiological pH. The new materials have the common characteristic of being able to degrade by acid hydrolysis under conditions commonly found within the endosomal or lysosomal compartments of cells thereby releasing their payload within the cell. The materials can also be used for the delivery of therapeutics to the acidic regions of tumors and other sites of inflammation.

Reducing unwanted trauma memories by imaginal exposure or autobiographical memory elaboration: An analogue study of memory processes

PubMed Central

Ehlers, Anke; Mauchnik, Jana; Handley, Rachel

2012-01-01

Unwanted memories of traumatic events are a core symptom of post-traumatic stress disorder. A range of interventions including imaginal exposure and elaboration of the trauma memory in its autobiographical context are effective in reducing such unwanted memories. This study explored whether priming for stimuli that occur in the context of trauma and evaluative conditioning may play a role in the therapeutic effects of these procedures. Healthy volunteers (N = 122) watched analogue traumatic and neutral picture stories. They were then randomly allocated to 20 min of either imaginal exposure, autobiographical memory elaboration, or a control condition designed to prevent further processing of the picture stories. A blurred picture identification task showed that neutral objects that preceded traumatic pictures in the stories were subsequently more readily identified than those that had preceded neutral stories, indicating enhanced priming. There was also an evaluative conditioning effect in that participants disliked neutral objects that had preceded traumatic pictures more. Autobiographical memory elaboration reduced the enhanced priming effect. Both interventions reduced the evaluative conditioning effect. Imaginal exposure and autobiographical memory elaboration both reduced the frequency of subsequent unwanted memories of the picture stories. PMID:21227404

Emotional Modulation of Learning and Memory: Pharmacological Implications.

PubMed

LaLumiere, Ryan T; McGaugh, James L; McIntyre, Christa K

2017-07-01

Memory consolidation involves the process by which newly acquired information becomes stored in a long-lasting fashion. Evidence acquired over the past several decades, especially from studies using post-training drug administration, indicates that emotional arousal during the consolidation period influences and enhances the strength of the memory and that multiple different chemical signaling systems participate in this process. The mechanisms underlying the emotional influences on memory involve the release of stress hormones and activation of the basolateral amygdala, which work together to modulate memory consolidation. Moreover, work suggests that this amygdala-based memory modulation occurs with numerous types of learning and involves interactions with many different brain regions to alter consolidation. Additionally, studies suggest that emotional arousal and amygdala activity in particular influence synaptic plasticity and associated proteins in downstream brain regions. This review considers the historical understanding for memory modulation and cellular consolidation processes and examines several research areas currently using this foundational knowledge to develop therapeutic treatments. Copyright © 2017 by The American Society for Pharmacology and Experimental Therapeutics.

Preparation and characterization of triple shape memory composite foams.

PubMed

Nejad, Hossein Birjandi; Baker, Richard M; Mather, Patrick T

2014-10-28

Foams prepared from shape memory polymers (SMPs) offer the potential for low density materials that can be triggered to deploy with a large volume change, unlike their solid counterparts that do so at near-constant volume. While examples of shape memory foams have been reported in the past, they have been limited to dual SMPs: those polymers featuring one switching transition between an arbitrarily programmed shape and a single permanent shape established by constituent crosslinks. Meanwhile, advances by SMP researchers have led to several approaches toward triple- or multi-shape polymers that feature more than one switching phase and thus a multitude of temporary shapes allowing for a complex sequence of shape deployments. Here, we report the design, preparation, and characterization of a triple shape memory polymeric foam that is open cell in nature and features a two phase, crosslinked SMP with a glass transition temperature of one phase at a temperature lower than a melting transition of the second phase. The soft materials were observed to feature high fidelity, repeatable triple shape behavior, characterized in compression and demonstrated for complex deployment by fixing a combination of foam compression and bending. We further explored the wettability of the foams, revealing composition-dependent behavior favorable for future work in biomedical investigations.

Solvent stimulated actuation of polyurethane-based shape memory polymer foams using dimethyl sulfoxide and ethanol

NASA Astrophysics Data System (ADS)

Boyle, A. J.; Weems, A. C.; Hasan, S. M.; Nash, L. D.; Monroe, M. B. B.; Maitland, D. J.

2016-07-01

Solvent exposure has been investigated to trigger actuation of shape memory polymers (SMPs) as an alternative to direct heating. This study aimed to investigate the feasibility of using dimethyl sulfoxide (DMSO) and ethanol (EtOH) to stimulate polyurethane-based SMP foam actuation and the required solvent concentrations in water for rapid actuation of hydrophobic SMP foams. SMP foams exhibited decreased T g when submerged in DMSO and EtOH when compared to water submersion. Kinetic DMA experiments showed minimal or no relaxation for all SMP foams in water within 30 min, while SMP foams submerged in EtOH exhibited rapid relaxation within 1 min of submersion. SMP foams expanded rapidly in high concentrations of DMSO and EtOH solutions, where complete recovery over 30 min was observed in DMSO concentrations greater than 90% and in EtOH concentrations greater than 20%. This study demonstrates that both DMSO and EtOH are effective at triggering volume recovery of polyurethane-based SMP foams, including in aqueous environments, and provides promise for use of this actuation technique in various applications.

Self-fitting shape memory polymer foam inducing bone regeneration: A rabbit femoral defect study.

PubMed

Xie, Ruiqi; Hu, Jinlian; Hoffmann, Oskar; Zhang, Yuanchi; Ng, Frankie; Qin, Tingwu; Guo, Xia

2018-04-01

Although tissue engineering has been attracted greatly for healing of critical-sized bone defects, great efforts for improvement are still being made in scaffold design. In particular, bone regeneration would be enhanced if a scaffold precisely matches the contour of bone defects, especially if it could be implanted into the human body conveniently and safely. In this study, polyurethane/hydroxyapatite-based shape memory polymer (SMP) foam was fabricated as a scaffold substrate to facilitate bone regeneration. The minimally invasive delivery and the self-fitting behavior of the SMP foam were systematically evaluated to demonstrate its feasibility in the treatment of bone defects in vivo. Results showed that the SMP foam could be conveniently implanted into bone defects with a compact shape. Subsequently, it self-matched the boundary of bone defects upon shape-recovery activation in vivo. Micro-computed tomography determined that bone ingrowth initiated at the periphery of the SMP foam with a constant decrease towards the inside. Successful vascularization and bone remodeling were also demonstrated by histological analysis. Thus, our results indicate that the SMP foam demonstrated great potential for bone regeneration. Copyright © 2018 Elsevier B.V. All rights reserved.

Effect of Cross-linking Density on Creep and Recovery Behavior in Epoxy-Based Shape Memory Polymers (SMEPs) for Structural Applications

NASA Astrophysics Data System (ADS)

Rao, Kavitha V.; Ananthapadmanabha, G. S.; Dayananda, G. N.

2016-12-01

Epoxy-based shape memory polymers (SMEPs) are gaining importance in the area of aerospace structures due to their high strength and stiffness which is a primary requirement for an SMEP in structural applications. The understanding of viscoelastic behavior of SMEPs is very essential to assess their shape memory effect. In the present work, three types of SMEPs with varying cross-linking densities were developed by curing an aromatic epoxy resin with aliphatic amines. Glass transition temperature ( T g) was measured for these SMEPs using advanced rheometric expansion system, and from the T g measurements, a range of temperatures from glassy to rubbery regimes were chosen. At selected temperatures, creep-recovery tests were performed in order to evaluate the viscoelastic behavior of SMEPs and also to investigate the effect of temperature on creep-recovery. Further, a three-parameter viscoelastic model (Zener) was used to fit the data obtained from experiments. Model parameters like moduli of the springs and viscosity of the dashpot were evaluated by curve fitting. Results revealed that Zener model was well suited to describe the viscoelastic behavior of SMEPs as a function of test temperatures.

Trehalose Glycopolymer Enhances Both Solution Stability and Pharmacokinetics of a Therapeutic Protein.

PubMed

Liu, Yang; Lee, Juneyoung; Mansfield, Kathryn M; Ko, Jeong Hoon; Sallam, Sahar; Wesdemiotis, Chrys; Maynard, Heather D

2017-03-15

Biocompatible polymers such as poly(ethylene glycol) (PEG) have been successfully conjugated to therapeutic proteins to enhance their pharmacokinetics. However, many of these polymers, including PEG, only improve the in vivo lifetimes and do not protect proteins against inactivation during storage and transportation. Herein, we report a polymer with trehalose side chains (PolyProtek) that is capable of improving both the external stability and the in vivo plasma half-life of a therapeutic protein. Insulin was employed as a model biologic, and high performance liquid chromatography and dynamic light scattering confirmed that addition of trehalose glycopolymer as an excipient or covalent conjugation prevented thermal or agitation-induced aggregation of insulin. The insulin-trehalose glycopolymer conjugate also showed significantly prolonged plasma circulation time in mice, similar to the analogous insulin-PEG conjugate. The insulin-trehalose glycopolymer conjugate was active as tested by insulin tolerance tests in mice and retained bioactivity even after exposure to high temperatures. The trehalose glycopolymer was shown to be nontoxic to mice up to at least 1.6 mg/kg dosage. These results together suggest that the trehalose glycopolymer should be further explored as an alternative to PEG for long circulating protein therapeutics.

Polymer Self-Assembled Nanostructures as Innovative Drug Nanocarrier Platforms.

PubMed

Pippa, Natassa; Pispas, Stergios; Demetzos, Costas

2016-01-01

Polymer self-assembled nanostructures are used in pharmaceutical sciences as bioactive molecules' delivery systems for therapeutic and diagnostic purposes. Micelles, polyelectrolyte complexes, polymersomes, polymeric nanoparticles, nanogels and polymer grafted liposomes represent delivery vehicles that are marketed and/or under clinical development, as drug formulations. In this mini-review, these, recently appeared in the literature, innovative polymer drug nanocarrier platforms are discussed, starting from their technological development in the laboratory to their potential clinical use, through studies of their biophysics, thermodynamics, physical behavior, morphology, bio-mimicry, therapeutic efficacy and safety. The properties of an ideal drug delivery system are the structural control over size and shape of drug or imaging agent cargo/domain, biocompatibility, nontoxic polymer/ pendant functionality and the precise, nanoscale container and/or scaffolding properties with high drug or imaging agent capacity features. Self-assembled polymer nanostructures exhibit all these properties and could be considered as ideal drug nanocarriers through control of their size, structure and morphology, with the aid of a large variety of parameters, in vitro and in vivo. These modern trends reside at the interface of soft matter self-assembly and pharmaceutical sciences and the technologies for health. Great advantages related to basic science and applications are expected by understanding the self-assembly behavior of these polymeric nanotechnological drug delivery systems, created through bio-inspiration and biomimicry and have potential utilization into clinical applications.

Memory reconsolidation and psychotherapeutic process.

PubMed

Liberzon, Israel; Javanbakht, Arash

2015-01-01

Lane et al. propose a heuristic model in which distinct, and seemingly irreconcilable, therapies can coexist. Authors postulate that memory reconsolidation is a key common neurobiological process mediating the therapeutic effects. This conceptualization raises a set of important questions regarding neuroscience and translational aspects of fear memory reconsolidation. We discuss the implications of the target article's memory reconsolidation model in the development of more effective interventions, and in the identification of less effective, or potentially harmful approaches, as well as concepts of contextualization, optimal arousal, and combined therapy.

Complexation of amyloid fibrils with charged conjugated polymers.

PubMed

Ghosh, Dhiman; Dutta, Paulami; Chakraborty, Chanchal; Singh, Pradeep K; Anoop, A; Jha, Narendra Nath; Jacob, Reeba S; Mondal, Mrityunjoy; Mankar, Shruti; Das, Subhadeep; Malik, Sudip; Maji, Samir K

2014-04-08

It has been suggested that conjugated charged polymers are amyloid imaging agents and promising therapeutic candidates for neurological disorders. However, very less is known about their efficacy in modulating the amyloid aggregation pathway. Here, we studied the modulation of Parkinson's disease associated α-synuclein (AS) amyloid assembly kinetics using conjugated polyfluorene polymers (PF, cationic; PFS, anionic). We also explored the complexation of these charged polymers with the various AS aggregated species including amyloid fibrils and oligomers using multidisciplinary biophysical techniques. Our data suggests that both polymers irrespective of their different charges in the side chains increase the fibrilization kinetics of AS and also remarkably change the morphology of the resultant amyloid fibrils. Both polymers were incorporated/aligned onto the AS amyloid fibrils as evident from electron microscopy (EM) and atomic force microscopy (AFM), and the resultant complexes were structurally distinct from their pristine form of both polymers and AS supported by FTIR study. Additionally, we observed that the mechanism of interactions between the polymers with different species of AS aggregates were markedly different.

Strategies Toward Well-Defined Polymer Nanoparticles Inspired by Nature: Chemistry versus Versatility

PubMed Central

Elsabahy, Mahmoud; Wooley, Karen L.

2014-01-01

Polymeric nanoparticles are promising delivery platforms for various biomedical applications. One of the main challenges toward the development of therapeutic nanoparticles is the premature disassembly and release of the encapsulated drug. Among the different strategies to enhance the kinetic stability of polymeric nanoparticles, shell- and core-crosslinking have been shown to provide robust character, while creating a suitable environment for encapsulation of a wide range of therapeutics, including hydrophilic, hydrophobic, metallic, and small and large biomolecules, with gating of their release as well. The versatility of shell- and core-crosslinked nanoparticles is driven from the ease by which the structures of the shell- and core-forming polymers and crosslinkers can be modified. In addition, postmodification with cell-recognition moieties, grafting of antibiofouling polymers, or chemical degradation of the core to yield nanocages allow the use of these robust nanostructures as “smart” nanocarriers. The building principles of these multifunctional nanoparticles borrow analogy from the synthesis, supramolecular assembly, stabilization, and dynamic activity of the naturally driven biological nanoparticles such as proteins, lipoproteins, and viruses. In this review, the chemistry involved during the buildup from small molecules to polymers to covalently stabilized nanoscopic objects is detailed, with contrast of the strategies of the supramolecular assembly of polymer building blocks followed by intramicellar stabilization into shell-, core-, or core–shell-crosslinked knedel-like nanoparticles versus polymerization of polymers into nanoscopic molecular brushes followed by further intramolecular covalent stabilization events. The rational design of shell-crosslinked knedel-like nanoparticles is then elaborated for therapeutic packaging and delivery, with emphasis on the polymer chemistry aspects to accomplish the synthesis of such nanoparticulate systems

New trends in the optical and electronic applications of polymers containing transition-metal complexes.

PubMed

Liu, Shu-Juan; Chen, Yang; Xu, Wen-Juan; Zhao, Qiang; Huang, Wei

2012-04-13

Polymers containing transition-metal complexes exhibit excellent optical and electronic properties, which are different from those of polymers with a pure organic skeleton and combine the advantages of both polymers and metal complexes. Hence, research about this class of polymers has attracted more and more interest in recent years. Up to now, a number of novel polymers containing transition-metal complexes have been exploited, and significant advances in their optical and electronic applications have been achieved. In this article, we summarize some new research trends in the applications of this important class of optoelectronic polymers, such as chemo/biosensors, electronic memory devices and photovoltaic devices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Acid-Responsive Therapeutic Polymer for Prolonging Nanoparticle Circulation Lifetime and Destroying Drug-Resistant Tumors.

PubMed

Piao, Ji-Gang; Gao, Feng; Yang, Lihua

2016-01-13

How to destroy drug-resistant tumor cells remains an ongoing challenge for cancer treatment. We herein report on a therapeutic nanoparticle, aHLP-PDA, which has an acid-activated hemolytic polymer (aHLP) grafted onto photothermal polydopamine (PDA) nanosphere via boronate ester bond, in efforts to ablate drug-resistant tumors. Upon exposure to oxidative stress and/or near-infrared laser irradiation, aHLP-PDA nanoparticle responsively releases aHLP, likely via responsive cleavage of boronate ester bond, and thus responsively exhibits acid-facilitated mammalian-membrane-disruptive activity. In vitro cell studies with drug-resistant and/or thermo-tolerant cancer cells show that the aHLP-PDA nanoparticle demonstrates preferential cytotoxicity at acidic pH over physiological pH. When administered intravenously, the aHLP-PDA nanoparticle exhibits significantly prolonged blood circulation lifetime and enhanced tumor uptake compared to bare PDA nanosphere, likely owing to aHLP's stealth effects conferred by its zwitterionic nature at blood pH. As a result, the aHLP-PDA nanoparticle effectively ablates drug-resistant tumors, leading to 100% mouse survival even on the 32nd day after suspension of photothermal treatment, as demonstrated with the mouse model. This work suggests that a combination of nanotechnology with lessons learned in bacterial antibiotic resistance may offer a feasible and effective strategy for treating drug-resistant cancers often found in relapsing patients.

Investigation on adaptive wing structure based on shape memory polymer composite hinge

NASA Astrophysics Data System (ADS)

Yu, Yuemin; Li, Xinbo; Zhang, Wei; Leng, Jinsong

2007-07-01

This paper describes the design and investigation of the SMP composite hinge and the morphing wing structure. The SMP composite hinge was based on SMP and carbon fiber fabric. The twisting recoverability of it was investigated by heating and then cooling repeatedly above and below the Tg. The twisting recoverability characterized by the twisting angle. Results show that the SMP composite hinge have good shape recoverability, Recovery time has a great influence on the twisting recoverability. The twisting recovery ratio became large with the increment of recovery time. The morphing wing can changes shape for different tasks. For the advantages of great recovery force and stable performances, we adopt SMP composite hinge as actuator to apply into the structure of the wing which can realize draw back wings to change sweep angle according to the speed and other requirements of military airplanes. Finally, a series of simulations and experiments are performed to investigate the deformations of morphing wings have been performed successfully. It can be seen that the sweep angle change became large with the increment of initial angle. The area reduction became large with the increment of initial angle, but after 75° the area reduction became smaller and smaller. The deformations of the triangle wing became large with the increment of temperature. The area and the sweep angle of wings can be controlled by adjusting the stimulate temperature and the initial twisting angle of shape memory polymer composite hinge.

Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications.

PubMed

Miao, Shida; Zhu, Wei; Castro, Nathan J; Leng, Jinsong; Zhang, Lijie Grace

2016-10-01

The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term "4D printing" refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from -8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at -18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and development of

Four-Dimensional Printing Hierarchy Scaffolds with Highly Biocompatible Smart Polymers for Tissue Engineering Applications

PubMed Central

Miao, Shida; Zhu, Wei; Castro, Nathan J.; Leng, Jinsong

2016-01-01

The objective of this study was to four-dimensional (4D) print novel biomimetic gradient tissue scaffolds with highly biocompatible naturally derived smart polymers. The term “4D printing” refers to the inherent smart shape transformation of fabricated constructs when implanted minimally invasively for seamless and dynamic integration. For this purpose, a series of novel shape memory polymers with excellent biocompatibility and tunable shape changing effects were synthesized and cured in the presence of three-dimensional printed sacrificial molds, which were subsequently dissolved to create controllable and graded porosity within the scaffold. Surface morphology, thermal, mechanical, and biocompatible properties as well as shape memory effects of the synthesized smart polymers and resultant porous scaffolds were characterized. Fourier transform infrared spectroscopy and gel content analysis confirmed the formation of chemical crosslinking by reacting polycaprolactone triol and castor oil with multi-isocyanate groups. Differential scanning calorimetry revealed an adjustable glass transition temperature in a range from −8°C to 35°C. Uniaxial compression testing indicated that the obtained polymers, possessing a highly crosslinked interpenetrating polymeric networks, have similar compressive modulus to polycaprolactone. Shape memory tests revealed that the smart polymers display finely tunable recovery speed and exhibit greater than 92% shape fixing at −18°C or 0°C and full shape recovery at physiological temperature. Scanning electron microscopy analysis of fabricated scaffolds revealed a graded microporous structure, which mimics the nonuniform distribution of porosity found within natural tissues. With polycaprolactone serving as a control, human bone marrow-derived mesenchymal stem cell adhesion, proliferation, and differentiation greatly increased on our novel smart polymers. The current work will significantly advance the future design and

A 1D thermomechanical network transition constitutive model coupled with multiple structural relaxation for shape memory polymers

NASA Astrophysics Data System (ADS)

Zeng, Hao; Xie, Zhimin; Gu, Jianping; Sun, Huiyu

2018-03-01

A new thermomechanical network transition constitutive model is proposed in the study to describe the viscoelastic behavior of shape memory polymers (SMPs). Based on the microstructure of semi-crystalline SMPs, a new simplified transformation equation is proposed to describe the transform of transient networks. And the generalized fractional Maxwell model is introduced in the paper to estimate the temperature-dependent storage modulus. In addition, a neo-KAHR theory with multiple discrete relaxation processes is put forward to study the structural relaxation of the nonlinear thermal strain in cooling/heating processes. The evolution equations of the time- and temperature-dependent stress and strain response are developed. In the model, the thermodynamical and mechanical characteristics of SMPs in the typical thermomechanical cycle are described clearly and the irreversible deformation is studied in detail. Finally, the typical thermomechanical cycles are simulated using the present constitutive model, and the simulation results agree well with the experimental results.

Technical Operations Support III (TOPS III). Task Order 0018: Nanostructured Graphene-Like Polymers

DTIC Science & Technology

2010-06-01

diverse response by a large class of materials: viscoelastic fluids, inelasticity, crystallization of polymers, twinning, shape memory alloys , single...crystal super alloys , and viscoelastic solids. 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT: SAR 18. NUMBER...twinning (Rajagopal and Srinivasa (1997)), Kannan et al. (2002)), shape memory alloys (Rajagopal and Srinivasa (1999)), single crystal super alloys

Humidity-activated shape memory effect on plasticized starch-based biomaterials.

PubMed

Sessini, Valentina; Arrieta, Marina P; Fernández-Torres, Alberto; Peponi, Laura

2018-01-01

Humidity-activated shape memory behavior of plasticized starch-based films reinforced with the innovative combination of starch nanocrystals (SNCs) and catechin as antioxidant were studied. In a previous work, we reported the processing of gelatinized starch-based films filled with SNCs and catechin as antioxidant agent, and we observed that this novel combination leads to starch-based film with enhanced thermal and mechanical performance. In this work, the humidity-activated shape memory behavior of the previous developed starch-based films was characterized. The moisture loss as well as the moisture absorption were studied since they are essential parameters in humidity-activated shape memory polymers to fix the temporary shape and to recover the original shape, respectively. Therefore, the effect of the incorporation of SNCs and catechin on the humidity-activated shape memory properties of plasticized starch was also studied. Moreover, the effectiveness of catechin to increase the polymer stability under oxidative atmosphere and the thermo-mechanical relaxation of all the starch-based materials were studied. The combination of plasticized starch matrix loaded with both, SNCs and catechin, leads to a multifunctional starch-based films with increased hydrophilicity and with excellent humidity-activated shape memory behavior with interest for potential biomedical applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Direct-write fabrication of 4D active shape-changing behavior based on a shape memory polymer and its nanocomposite (Conference Presentation)

NASA Astrophysics Data System (ADS)

Wei, Hongqiu; Zhang, Qiwei; Yao, Yongtao; Liu, Liwu; Liu, Yanju; Leng, Jinsong

2017-04-01

Shape memory polymers (SMPs), a typical class of smart materials, have been witnessed significant advances in the past decades. Based on the unique performance to recover the initial shape after going through a shape deformation, the applications of SMPs have aroused growing interests. However, most of the researches are hindered by traditional processing technologies which limit the design space of SMPs-based structures. Three-dimension (3D) printing as an emerging technology endows design freedom to manufacture materials with complex structures. In present article, we show that by employing direct-write printing method; one can realize the printing of SMPs to achieve 4D active shape-changing structures. We first fabricated a kind of 3D printable polylactide (PLA)-based SMPs and characterized the overall properties of such materials. Results demonstrated the prepared PLA-based SMPs presenting excellent shape memory effect. In what follows, the rheological properties of such PLA-based SMP ink during printing process were discussed in detail. Finally, we designed and printed several 3D configurations for investigation. By combining 3D printing with shape memory behavior, these printed structures achieve 4D active shape-changing performance under heat stimuli. This research presents a high flexible method to realize the fabrication of SMP-based 4D active shape-changing structures, which opens the way for further developments and improvements of high-tech fields like 4D printing, soft robotics, micro-systems and biomedical devices.

Ion conducting organic/inorganic hybrid polymers

NASA Technical Reports Server (NTRS)

Meador, Maryann B. (Inventor); Kinder, James D. (Inventor)

2010-01-01

This invention relates to a series of organic/inorganic hybrid polymers that are easy to fabricate into dimensionally stable films with good ion-conductivity over a wide range of temperatures for use in a variety of applications. The polymers are prepared by the reaction of amines, preferably diamines and mixtures thereof with monoamines with epoxy-functionalized alkoxysilanes. The products of the reaction are polymerized by hydrolysis of the alkoxysilane groups to produce an organic-containing silica network. Suitable functionality introduced into the amine and alkoxysilane groups produce solid polymeric membranes which conduct ions for use in fuel cells, high-performance solid state batteries, chemical sensors, electrochemical capacitors, electro-chromic windows or displays, analog memory devices and the like.

Light-Induced Temperature Transitions in Biodegradable Polymer and Nanorod Composites**

PubMed Central

Hribar, Kolin C.; Metter, Robert B.; Ifkovits, Jamie L.; Troxler, Thomas

2010-01-01

Shape-memory materials (including polymers, metals, and ceramics) are those that are processed into a temporary shape and respond to some external stimuli (e.g., temperature) to undergo a transition back to a permanent shape.[1, 2] Shape memory polymers are finding use in a range of applications from aerospace to fabrics, to biomedical devices and microsystem components.[3–5] For many applications, it would be beneficial to initiate heating with an external trigger (e.g., transdermal light exposure). In this work, we formulated composites of gold nanorods (<1% by volume) and biodegradable networks, where exposure to infrared light induced heating and consequently, shape transitions. The heating is repeatable and tunable based on nanorod concentration and light intensity and the nanorods did not alter the cytotoxicity or in vivo tissue response to the networks. PMID:19408258

Polymers in cell encapsulation from an enveloped cell perspective.

PubMed

de Vos, Paul; Lazarjani, Hamideh Aghajani; Poncelet, Denis; Faas, Marijke M

2014-04-01

In the past two decades, many polymers have been proposed for producing immunoprotective capsules. Examples include the natural polymers alginate, agarose, chitosan, cellulose, collagen, and xanthan and synthetic polymers poly(ethylene glycol), polyvinyl alcohol, polyurethane, poly(ether-sulfone), polypropylene, sodium polystyrene sulfate, and polyacrylate poly(acrylonitrile-sodium methallylsulfonate). The biocompatibility of these polymers is discussed in terms of tissue responses in both the host and matrix to accommodate the functional survival of the cells. Cells should grow and function in the polymer network as adequately as in their natural environment. This is critical when therapeutic cells from scarce cadaveric donors are considered, such as pancreatic islets. Additionally, the cell mass in capsules is discussed from the perspective of emerging new insights into the release of so-called danger-associated molecular pattern molecules by clumps of necrotic therapeutic cells. We conclude that despite two decades of intensive research, drawing conclusions about which polymer is most adequate for clinical application is still difficult. This is because of the lack of documentation on critical information, such as the composition of the polymer, the presence or absence of confounding factors that induce immune responses, toxicity to enveloped cells, and the permeability of the polymer network. Only alginate has been studied extensively and currently qualifies for application. This review also discusses critical issues that are not directly related to polymers and are not discussed in the other reviews in this issue, such as the functional performance of encapsulated cells in vivo. Physiological endocrine responses may indeed not be expected because of the many barriers that the metabolites encounter when traveling from the blood stream to the enveloped cells and back to circulation. However, despite these diffusion barriers, many studies have shown optimal

Current Advances in Polymer-Based Nanotheranostics for Cancer Treatment and Diagnosis

PubMed Central

2015-01-01

Nanotheranostics is a relatively new, fast-growing field that combines the advantages of treatment and diagnosis via a single nanoscale carrier. The ability to bundle both therapeutic and diagnostic capabilities into one package offers exciting prospects for the development of novel nanomedicine. Nanotheranostics can deliver treatment while simultaneously monitoring therapy response in real-time, thereby decreasing the potential of over- or under-dosing patients. Polymer-based nanomaterials, in particular, have been used extensively as carriers for both therapeutic and bioimaging agents and thus hold great promise for the construction of multifunctional theranostic formulations. Herein, we review recent advances in polymer-based systems for nanotheranostics, with a particular focus on their applications in cancer research. We summarize the use of polymer nanomaterials for drug delivery, gene delivery, and photodynamic therapy, combined with imaging agents for magnetic resonance imaging, radionuclide imaging, and fluorescence imaging. PMID:25014486

Influence of therapeutic radiation on polycaprolactone and polyurethane biomaterials.

PubMed

Cooke, Shelley L; Whittington, Abby R

2016-03-01

Biomedical polymers are exposed in vivo to ionizing radiation as implants, coatings and bystander materials. High levels of ionizing radiation (e.g. X-ray and gamma) have been reported to cause degradation and/or cross-linking in many polymers. This pilot study sought to determine causes of failure, by investigating how therapeutic radiation affects two different porous polymeric scaffolds: polycaprolactone (PCL) and polyurethane (PU). PCL is a bioresorbable material used in biomedical devices (e.g., dentistry, internal fixation devices and targeted drug delivery capsules). PU is commonly used in medical applications (e.g., coatings for pacemakers, tissue expanders, catheter tubing and wound dressings). PU was specifically fabricated to be a non-degradable polymer in this study. Porous scaffolds, fabricated using solvent casting and/or salt leeching techniques, were placed in phosphate buffered saline (PBS, pH=7.4) and exposed to typical cancer radiotherapy. A total dose of 50 Gy was broken into 25 doses over an eleven-week period. Collected PBS was tested for polymer leachants and degradation products using Gas Chromatography Mass Spectroscopy (GC-MS), results revealed no analyzable leachants from either polymer. Scaffolds were characterized using Environmental Scanning Electron Microscopy, Size-exclusion chromatography (SEC), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared Spectroscopy (FTIR). No gross visual changes were observed in either polymer, however PU exhibited microstructure changes after irradiation. Increased number average molecular weight and weight average molecular weight in PCL and PU were observed after irradiation, indicating crosslinking. PU displayed an increase in intrinsic viscosity that further confirms increased crosslinking. PCL and PU showed decreases in crystallinity after irradiation, and PU crystallinity shifted from long-range-order hard segments to short-range-order hard segments after irradiation. Results

Polymer and ceramic nanocomposites for aerospace applications

NASA Astrophysics Data System (ADS)

Rathod, Vivek T.; Kumar, Jayanth S.; Jain, Anjana

2017-11-01

This paper reviews the potential of polymer and ceramic matrix composites for aerospace/space vehicle applications. Special, unique and multifunctional properties arising due to the dispersion of nanoparticles in ceramic and metal matrix are briefly discussed followed by a classification of resulting aerospace applications. The paper presents polymer matrix composites comprising majority of aerospace applications in structures, coating, tribology, structural health monitoring, electromagnetic shielding and shape memory applications. The capabilities of the ceramic matrix nanocomposites to providing the electromagnetic shielding for aircrafts and better tribological properties to suit space environments are discussed. Structural health monitoring capability of ceramic matrix nanocomposite is also discussed. The properties of resulting nanocomposite material with its disadvantages like cost and processing difficulties are discussed. The paper concludes after the discussion of the possible future perspectives and challenges in implementation and further development of polymer and ceramic nanocomposite materials.

The "memory kinases": roles of PKC isoforms in signal processing and memory formation.

PubMed

Sun, Miao-Kun; Alkon, Daniel L

2014-01-01

The protein kinase C (PKC) isoforms, which play an essential role in transmembrane signal conduction, can be viewed as a family of "memory kinases." Evidence is emerging that they are critically involved in memory acquisition and maintenance, in addition to their involvement in other functions of cells. Deficits in PKC signal cascades in neurons are one of the earliest abnormalities in the brains of patients suffering from Alzheimer's disease. Their dysfunction is also involved in several other types of memory impairments, including those related to emotion, mental retardation, brain injury, and vascular dementia/ischemic stroke. Inhibition of PKC activity leads to a reduced capacity of many types of learning and memory, but may have therapeutic values in treating substance abuse or aversive memories. PKC activators, on the other hand, have been shown to possess memory-enhancing and antidementia actions. PKC pharmacology may, therefore, represent an attractive area for developing effective cognitive drugs for the treatment of many types of memory disorders and dementias. © 2014 Elsevier Inc. All rights reserved.

Long-term delivery of protein therapeutics.

PubMed

Vaishya, Ravi; Khurana, Varun; Patel, Sulabh; Mitra, Ashim K

2015-03-01

Proteins are effective biotherapeutics with applications in diverse ailments. Despite being specific and potent, their full clinical potential has not yet been realized. This can be attributed to short half-lives, complex structures, poor in vivo stability, low permeability, frequent parenteral administrations and poor adherence to treatment in chronic diseases. A sustained release system, providing controlled release of proteins, may overcome many of these limitations. This review focuses on recent development in approaches, especially polymer-based formulations, which can provide therapeutic levels of proteins over extended periods. Advances in particulate, gel-based formulations and novel approaches for extended protein delivery are discussed. Emphasis is placed on dosage form, method of preparation, mechanism of release and stability of biotherapeutics. Substantial advancements have been made in the field of extended protein delivery via various polymer-based formulations over last decade despite the unique delivery-related challenges posed by protein biologics. A number of injectable sustained-release formulations have reached market. However, therapeutic application of proteins is still hampered by delivery-related issues. A large number of protein molecules are under clinical trials, and hence, there is an urgent need to develop new methods to deliver these highly potent biologics.

Characterizing and modeling the free recovery and constrained recovery behavior of a polyurethane shape memory polymer

NASA Astrophysics Data System (ADS)

Volk, Brent L.; Lagoudas, Dimitris C.; Maitland, Duncan J.

2011-09-01

In this work, tensile tests and one-dimensional constitutive modeling were performed on a high recovery force polyurethane shape memory polymer that is being considered for biomedical applications. The tensile tests investigated the free recovery (zero load) response as well as the constrained displacement recovery (stress recovery) response at extension values up to 25%, and two consecutive cycles were performed during each test. The material was observed to recover 100% of the applied deformation when heated at zero load in the second thermomechanical cycle, and a stress recovery of 1.5-4.2 MPa was observed for the constrained displacement recovery experiments. After the experiments were performed, the Chen and Lagoudas model was used to simulate and predict the experimental results. The material properties used in the constitutive model—namely the coefficients of thermal expansion, shear moduli, and frozen volume fraction—were calibrated from a single 10% extension free recovery experiment. The model was then used to predict the material response for the remaining free recovery and constrained displacement recovery experiments. The model predictions match well with the experimental data.

Versatile Loading of Diverse Cargo into Functional Polymer Capsules.

PubMed

Richardson, Joseph J; Maina, James W; Ejima, Hirotaka; Hu, Ming; Guo, Junling; Choy, Mei Y; Gunawan, Sylvia T; Lybaert, Lien; Hagemeyer, Christoph E; De Geest, Bruno G; Caruso, Frank

2015-02-01

Polymer microcapsules are of particular interest for applications including self-healing coatings, catalysis, bioreactions, sensing, and drug delivery. The primary way that polymer capsules can exhibit functionality relevant to these diverse fields is through the incorporation of functional cargo in the capsule cavity or wall. Diverse functional and therapeutic cargo can be loaded into polymer capsules with ease using polymer-stabilized calcium carbonate (CaCO 3 ) particles. A variety of examples are demonstrated, including 15 types of cargo, yielding a toolbox with effectively 500+ variations. This process uses no harsh reagents and can take less than 30 min to prepare, load, coat, and form the hollow capsules. For these reasons, it is expected that the technique will play a crucial role across scientific studies in numerous fields.

Polydopamine Particle-Filled Shape-Memory Polyurethane Composites with Fast Near-Infrared Light Responsibility.

PubMed

Yang, Li; Tong, Rui; Wang, Zhanhua; Xia, Hesheng

2018-03-25

A new kind of fast near-infrared (NIR) light-responsive shape-memory polymer composites was prepared by introducing polydopamine particles (PDAPs) into commercial shape-memory polyurethane (SMPU). The toughness and strength of the polydopamine-particle-filled polyurethane composites (SMPU-PDAPs) were significantly enhanced with the addition of PDAPs due to the strong interface interaction between PDAPs and polyurethane segments. Owing to the outstanding photothermal effect of PDAPs, the composites exhibit a rapid light-responsive shape-memory process in 60 s with a PDAPs content of 0.01 wt%. Due to the excellent dispersion and convenient preparation method, PDAPs have great potential to be used as high-efficiency and environmentally friendly fillers to obtain novel photoactive functional polymer composites. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effects of fiber pre-strain on the healing efficiency of thermoset polymers

NASA Astrophysics Data System (ADS)

Ajisafe, Oludayo

One major challenge that has been facing material self healing is how to heal bigger macroscopic or structural scale damage autonomously, repeatedly, efficiently and at molecular length scale. Different approaches have been used to heal materials. However, none of them can heal macroscopic cracks. Our research group has proposed a novel shape-memory polymer (SMP) based, bio-inspired Close-Then-Heal (CTH) scheme to heal macroscopic cracks in SMP matrix. The most recent development in our group is to use SMP fibers to heal conventional thermosetting polymers according to the CTH scheme. The aim of this study is to further investigate the effect of pre-tension of SMP fibers during the cold-drawing programming on the self-healing efficiency of the conventional thermosetting polymer composites. This was done by fabricating a composite with thermoplastic particles (polycaprolactone) dispersed in a thermosetting polymer matrix (Epon 828). Shape memory fiber pre-tensioned into 3 different groups of 0%, 50% and 100% prestrain, was also embedded into the composite in the longitudinal direction. In this composite, the shape memory effect of the shape memory fibers is utilized for sealing (closing) the cracks and the thermoplastic particles are used for molecular-length scale healing. In this study, 7% by volume of thermoplastic particles was used. Beam specimens were prepared and controlled structural length scale damage was created prior to curing by inserting an aluminum foil of designed thickness in a perpendicular direction to the shape memory fibers before the matrix was allowed to cure. The aluminum sheet was removed post cure to leave a controlled damage. The specimen was healed by fixing the two ends of the beam and heating the sample above the Tg of the shape memory fiber. The recovery force of the sample was recorded and then the beam was tested again to fracture. This fracture healing cycle lasted 7 times. The healing efficiency was evaluated per the peak

Supplement request for Support of MRS Symposium (PECASE: Active Microstructured Polymer Systems)

DTIC Science & Technology

2015-07-06

materials (e.g., gels, polymers, liquids , liquid crystals and photosensitive materials) that can change shape in a controlled response to stimuli. These...Rogers1. 1, , University of Illinois, Urbana, Illinois, USA. Show Abstract 8:45 AM - *XX1.02 New Wonders of Nafion : Shape Memory, Temperature Memory... Liquid Crystal Institute, Kent State University, Kent, Ohio, USA; 5, Department of Electrical and Computer Engineering, University of Idaho, Moscow

pH-Responsive Shape Memory Poly(ethylene glycol)-Poly(ε-caprolactone)-based Polyurethane/Cellulose Nanocrystals Nanocomposite.

PubMed

Li, Ying; Chen, Hongmei; Liu, Dian; Wang, Wenxi; Liu, Ye; Zhou, Shaobing

2015-06-17

In this study, we developed a pH-responsive shape-memory polymer nanocomposite by blending poly(ethylene glycol)-poly(ε-caprolactone)-based polyurethane (PECU) with functionalized cellulose nanocrystals (CNCs). CNCs were functionalized with pyridine moieties (CNC-C6H4NO2) through hydroxyl substitution of CNCs with pyridine-4-carbonyl chloride and with carboxyl groups (CNC-CO2H) via 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) mediated surface oxidation, respectively. At a high pH value, the CNC-C6H4NO2 had attractive interactions from the hydrogen bonding between pyridine groups and hydroxyl moieties; at a low pH value, the interactions reduced or disappeared due to the protonation of pyridine groups, which are a Lewis base. The CNC-CO2H responded to pH variation in an opposite manner. The hydrogen bonding interactions of both CNC-C6H4NO2 and CNC-CO2H can be readily disassociated by altering pH values, endowing the pH-responsiveness of CNCs. When these functionalized CNCs were added in PECU polymer matrix to form nanocomposite network which was confirmed with rheological measurements, the mechanical properties of PECU were not only obviously improved but also the pH-responsiveness of CNCs could be transferred to the nanocomposite network. The pH-sensitive CNC percolation network in polymer matrix served as the switch units of shape-memory polymers (SMPs). Furthermore, the modified CNC percolation network and polymer molecular chains also had strong hydrogen bonding interactions among hydroxyl, carboxyl, pyridine moieties, and isocyanate groups, which could be formed or destroyed through changing pH value. The shape memory function of the nanocomposite network was only dependent on the pH variation of the environment. Therefore, this pH-responsive shape-memory nancomposite could be potentially developed into a new smart polymer material.

Low density biodegradable shape memory polyurethane foams for embolic biomedical applications

PubMed Central

Singhal, Pooja; Small, Ward; Cosgriff-Hernandez, Elizabeth; Maitland, Duncan J; Wilson, Thomas S

2014-01-01

Low density shape memory polymer foams hold significant interest in the biomaterials community for their potential use in minimally invasive embolic biomedical applications. The unique shape memory behavior of these foams allows them to be compressed to a miniaturized form, which can be delivered to an anatomical site via a transcatheter process, and thereafter actuated to embolize the desired area. Previous work in this field has described the use of a highly covalently crosslinked polymer structure for maintaining excellent mechanical and shape memory properties at the application-specific ultra low densities. This work is aimed at further expanding the utility of these biomaterials, as implantable low density shape memory polymer foams, by introducing controlled biodegradability. A highly covalently crosslinked network structure was maintained by use of low molecular weight, symmetrical and polyfunctional hydroxyl monomers such as Polycaprolactone triol (PCL-t, Mn 900 g), N,N,N0,N0-Tetrakis (hydroxypropyl) ethylenediamine (HPED), and Tris (2-hydroxyethyl) amine (TEA). Control over the degradation rate of the materials was achieved by changing the concentration of the degradable PCL-t monomer, and by varying the material hydrophobicity. These porous SMP materials exhibit a uniform cell morphology and excellent shape recovery, along with controllable actuation temperature and degradation rate. We believe that they form a new class of low density biodegradable SMP scaffolds that can potentially be used as “smart” non-permanent implants in multiple minimally invasive biomedical applications. PMID:24090987

Conductive polymers for controlled release and treatment of central nervous system injury

NASA Astrophysics Data System (ADS)

Saigal, Rajiv

As one of the most devastating forms of neurotrauma, spinal cord injury remains a challenging clinical problem. The difficulties in treatment could potentially be resolved by better technologies for therapeutic delivery. In order to develop new approaches to treating central nervous system injury, this dissertation focused on using electrically-conductive polymers, controlled drug release, and stem cell transplantation. We first sought to enhance the therapeutic potential of neural stem cells by electrically increasing their production of neurotrophic factors (NTFs), important molecules for neuronal cell survival, differentiation, synaptic development, plasticity, and growth. We fabricated a new cell culture device for growing neural stem cells on a biocompatible, conductive polymer. Electrical stimulation via the polymer led to upregulation of NTF production by neural stem cells. This approach has the potential to enhance stem cell function while avoiding the pitfalls of genetic manipulation, possibly making stem cells more viable as a clinical therapy. Seeing the therapeutic potential of conductive polymers, we extended our studies to an in vivo model of spinal cord injury (SCI). Using a novel fabrication and extraction technique, a conductive polymer was fabricated to fit to the characteristic pathology that follows contusive SCI. Assessed via quantitative analysis of MR images, the conductive polymer significantly reduced compression of the injured spinal cord. Further characterizing astroglial and neuronal response of injured host tissue, we found significant neuronal sparing as a result of this treatment. The in vivo studies also demonstrated improved locomotor recovery mediated by a conductive polymer scaffold over a non-conductive control. We next sought to take advantage of conductive polymers for local, electronically-controlled release of drugs. Seeking to overcome reported limitations in drug delivery via polypyrrole, we first embedded drugs in poly

Large energy absorption in Ni-Mn-Ga/polymer composites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feuchtwanger, Jorge; Richard, Marc L.; Tang, Yun J.

2005-05-15

Ferromagnetic shape memory alloys can respond to a magnetic field or applied stress by the motion of twin boundaries and hence they show large hysteresis or energy loss. Ni-Mn-Ga particles made by spark erosion have been dispersed and oriented in a polymer matrix to form pseudo 3:1 composites which are studied under applied stress. Loss ratios have been determined from the stress-strain data. The loss ratios of the composites range from 63% to 67% compared to only about 17% for the pure, unfilled polymer samples.

Nonmuscle myosin IIB as a therapeutic target for the prevention of relapse to methamphetamine use

PubMed Central

Young, Erica J.; Blouin, Ashley M.; Briggs, Sherri B.; Sillivan, Stephanie E.; Lin, Li; Cameron, Michael D.; Rumbaugh, Gavin; Miller, Courtney A.

2015-01-01

Memories associated with drug use increase vulnerability to relapse in substance use disorder (SUD) and there are no pharmacotherapies for the prevention of relapse. Previously, we reported a promising finding that storage of memories associated with methamphetamine (METH), but not memories for fear or food reward, is vulnerable to disruption by actin depolymerization in the basolateral amygdala complex (BLC). However, actin is not a viable therapeutic target because of its numerous functions throughout the body. Here we report the discovery of a viable therapeutic target, nonmuscle myosin II (NMIIB), a molecular motor that supports memory by directly driving synaptic actin polymerization. A single intra-BLC treatment with Blebbistatin, a small molecule inhibitor of class II myosin isoforms, including NMIIB, produced a long-lasting disruption of context-induced drug seeking (at least 30 days). Further, post-consolidation genetic knockdown of Myh10, the heavy chain of the most highly expressed NMII in the BLC, was sufficient to produce METH-associated memory loss. Blebbistatin was found to be highly brain penetrant. A single systemic injection of the compound selectively disrupted the storage of METH-associated memory and reversed the accompanying increase in BLC spine density. This effect was specific to METH-associated memory, as it had no effect on an auditory fear memory. The effect was also independent of retrieval, as METH-associated memory was disrupted twenty-four hours after a single systemic injection of Blebbistatin delivered in the home cage. Together, these results argue for the further development of small molecule inhibitors of nonmuscle myosin II as potential therapeutics for the prevention of SUD relapse triggered by drug associations. PMID:26239291

Unravelling ``off-target'' effects of redox-active polymers and polymer multilayered capsules in prostate cancer cells

NASA Astrophysics Data System (ADS)

Beretta, Giovanni L.; Folini, Marco; Cavalieri, Francesca; Yan, Yan; Fresch, Enrico; Kaliappan, Subramanian; Hasenöhrl, Christoph; Richardson, Joseph J.; Tinelli, Stella; Fery, Andreas; Caruso, Frank; Zaffaroni, Nadia

2015-03-01

Redox-active polymers and carriers are oxidizing nanoagents that can potentially trigger intracellular off-target effects. In the present study, we investigated the occurrence of off-target effects in prostate cancer cells following exposure to redox-active polymer and thin multilayer capsules with different chemical properties. We show that, depending on the intracellular antioxidant capacity, thiol-functionalized poly(methacrylic acid), PMASH triggers cell defense responses/perturbations that result in off-target effects (i.e., induction of autophagy and down-regulation of survivin). Importantly, the conversion of the carboxyl groups of PMASH into the neutral amides of poly(hydroxypropylmetacrylamide) (pHPMASH) nullified the off-target effects and cytotoxicity in tested cell lines. This suggests that the simultaneous action of carboxyl and disulfide groups in PMASH polymer or capsules may play a role in mediating the intracellular off-target effects. Our work provides evidence that the rational design of redox-active carriers for therapeutic-related application should be guided by a careful investigation on potential disturbance of the cellular machineries related to the carrier association.Redox-active polymers and carriers are oxidizing nanoagents that can potentially trigger intracellular off-target effects. In the present study, we investigated the occurrence of off-target effects in prostate cancer cells following exposure to redox-active polymer and thin multilayer capsules with different chemical properties. We show that, depending on the intracellular antioxidant capacity, thiol-functionalized poly(methacrylic acid), PMASH triggers cell defense responses/perturbations that result in off-target effects (i.e., induction of autophagy and down-regulation of survivin). Importantly, the conversion of the carboxyl groups of PMASH into the neutral amides of poly(hydroxypropylmetacrylamide) (pHPMASH) nullified the off-target effects and cytotoxicity in tested cell

Effects of selective phosphodiesterases-4 inhibitors on learning and memory: a review of recent research.

PubMed

Peng, Sheng; Sun, Haiyan; Zhang, Xiaoqing; Liu, Gongjian; Wang, Guanglei

2014-09-01

Phosphodiesterase-4 (PDE-4) regulates the intracellular level of cyclic adenosine monophosphate. Recent studies demonstrated that PDE-4 inhibitors can counteract deficits in long-term memory caused by aging or increased expression of mutant forms of human amyloid precursor proteins, and can influence the process of memory function and cognitive enhancement. Therapeutics, such as ketamine, a drug used in clinical anesthesia, can also cause memory deficits as adverse effects. Targeting PDE-4 with selective inhibitors may offer a novel therapeutic strategy to prevent, slow the progress, and, eventually, treat memory deficits.

Creation of hydrophilic nitric oxide releasing polymers via plasma surface modification.

PubMed

Pegalajar-Jurado, A; Joslin, J M; Hawker, M J; Reynolds, M M; Fisher, E R

2014-08-13

Herein, we describe the surface modification of an S-nitrosated polymer derivative via H2O plasma treatment, resulting in polymer coatings that maintained their nitric oxide (NO) releasing capabilities, but exhibited dramatic changes in surface wettability. The poly(lactic-co-glycolic acid)-based hydrophobic polymer was nitrosated to achieve a material capable of releasing the therapeutic agent NO. The NO-loaded films were subjected to low-temperature H2O plasma treatments, where the treatment power (20-50 W) and time (1-5 min) were varied. The plasma treated polymer films were superhydrophilic (water droplet spread completely in <100 ms), yet retained 90% of their initial S-nitrosothiol content. Under thermal conditions, NO release profiles were identical to controls. Under buffer soak conditions, the NO release profile was slightly lowered for the plasma-treated materials; however, they still result in physiologically relevant NO fluxes. XPS, SEM-EDS, and ATR-IR characterization suggests the plasma treatment resulted in polymer rearrangement and implantation of hydroxyl and carbonyl functional groups. Plasma treated samples maintained both hydrophilic surface properties and NO release profiles after storage at -18 °C for at least 10 days, demonstrating the surface modification and NO release capabilities are stable over time. The ability to tune polymer surface properties while maintaining bulk properties and NO release properties, and the stability of those properties under refrigerated conditions, represents a unique approach toward creating enhanced therapeutic biopolymers.

Molecularly Engineered Polymer-Based Systems in Drug Delivery and Regenerative Medicine.

PubMed

Piluso, Susanna; Soultan, Al Halifa; Patterson, Jennifer

2017-01-01

Polymer-based systems are attractive in drug delivery and regenerative medicine due to the possibility of tailoring their properties and functions to a specific application. The present review provides several examples of molecularly engineered polymer systems, including stimuli responsive polymers and supramolecular polymers. The advent of controlled polymerization techniques has enabled the preparation of polymers with controlled molecular weight and well-defined architecture. By using these techniques coupled to orthogonal chemical modification reactions, polymers can be molecularly engineered to incorporate functional groups able to respond to small changes in the local environment or to a specific biological signal. This review highlights the properties and applications of stimuli-responsive systems and polymer therapeutics, such as polymer-drug conjugates, polymer-protein conjugates, polymersomes, and hyperbranched systems. The applications of polymeric membranes in regenerative medicine are also discussed. The examples presented in this review suggest that the combination of membranes with polymers that are molecularly engineered to respond to specific biological functions could be relevant in the field of regenerative medicine. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Shape Memory Polyurethane Materials Containing Ferromagnetic Iron Oxide and Graphene Nanoplatelets

PubMed Central

Urban, Magdalena

2017-01-01

Intelligent materials, such as memory shape polymers, have attracted considerable attention due to wide range of possible applications. Currently, intensive research is underway, in matters of obtaining memory shape materials that can be actuated via inductive methods, for example with help of magnetic field. In this work, an attempt was made to develop a new polymer composite—polyurethane modified with graphene nanoplates and ferromagnetic iron oxides—with improved mechanical properties and introduced magnetic and memory shape properties. Based on the conducted literature review, gathered data were compared to the results of similar materials. Obtained materials were tested for their thermal, rheological, mechanical and shape memory properties. Structure of both fillers and composites were also analyzed using various spectroscopic methods. The addition of fillers to the polyurethane matrix improved the mechanical and shape memory properties, without having a noticeable impact on thermal properties. As it was expected, the high content of fillers caused a significant change in viscosity of filled prepolymers (during the synthesis stage). Each of the studied composites showed better mechanical properties than the unmodified polyurethanes. The addition of magnetic particles introduced additional properties to the composite, which could significantly expand the functionality of the materials developed in this work. PMID:28906445

Shape Memory Polyurethane Materials Containing Ferromagnetic Iron Oxide and Graphene Nanoplatelets.

PubMed

Urban, Magdalena; Strankowski, Michał

2017-09-14

Intelligent materials, such as memory shape polymers, have attracted considerable attention due to wide range of possible applications. Currently, intensive research is underway, in matters of obtaining memory shape materials that can be actuated via inductive methods, for example with help of magnetic field. In this work, an attempt was made to develop a new polymer composite-polyurethane modified with graphene nanoplates and ferromagnetic iron oxides-with improved mechanical properties and introduced magnetic and memory shape properties. Based on the conducted literature review, gathered data were compared to the results of similar materials. Obtained materials were tested for their thermal, rheological, mechanical and shape memory properties. Structure of both fillers and composites were also analyzed using various spectroscopic methods. The addition of fillers to the polyurethane matrix improved the mechanical and shape memory properties, without having a noticeable impact on thermal properties. As it was expected, the high content of fillers caused a significant change in viscosity of filled prepolymers (during the synthesis stage). Each of the studied composites showed better mechanical properties than the unmodified polyurethanes. The addition of magnetic particles introduced additional properties to the composite, which could significantly expand the functionality of the materials developed in this work.

Cell microencapsulation with synthetic polymers

PubMed Central

Olabisi, Ronke M

2015-01-01

The encapsulation of cells into polymeric microspheres or microcapsules has permitted the transplantation of cells into human and animal subjects without the need for immunosuppressants. Cell-based therapies use donor cells to provide sustained release of a therapeutic product, such as insulin, and have shown promise in treating a variety of diseases. Immunoisolation of these cells via microencapsulation is a hotly investigated field, and the preferred material of choice has been alginate, a natural polymer derived from seaweed due to its gelling conditions. Although many natural polymers tend to gel in conditions favorable to mammalian cell encapsulation, there remain challenges such as batch to batch variability and residual components from the original source that can lead to an immune response when implanted into a recipient. Synthetic materials have the potential to avoid these issues; however, historically they have required harsh polymerization conditions that are not favorable to mammalian cells. As research into microencapsulation grows, more investigators are exploring methods to microencapsulate cells into synthetic polymers. This review describes a variety of synthetic polymers used to microencapsulate cells. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 846–859, 2015. PMID:24771675

Caspase-9 mediates synaptic plasticity and memory deficits of Danish dementia knock-in mice: caspase-9 inhibition provides therapeutic protection.

PubMed

Tamayev, Robert; Akpan, Nsikan; Arancio, Ottavio; Troy, Carol M; D'Adamio, Luciano

2012-12-10

Mutations in either Aβ Precursor protein (APP) or genes that regulate APP processing, such as BRI2/ITM2B and PSEN1/PSEN2, cause familial dementias. Although dementias due to APP/PSEN1/PSEN2 mutations are classified as familial Alzheimer disease (FAD) and those due to mutations in BRI2/ITM2B as British and Danish dementias (FBD, FDD), data suggest that these diseases have a common pathogenesis involving toxic APP metabolites. It was previously shown that FAD mutations in APP and PSENs promote activation of caspases leading to the hypothesis that aberrant caspase activation could participate in AD pathogenesis. Here, we tested whether a similar mechanism applies to the Danish BRI2/ITM2B mutation. We have generated a genetically congruous mouse model of FDD, called FDD(KI), which presents memory and synaptic plasticity deficits. We found that caspase-9 is activated in hippocampal synaptic fractions of FDD(KI) mice and inhibition of caspase-9 activity rescues both synaptic plasticity and memory deficits. These data directly implicate caspase-9 in the pathogenesis of Danish dementia and suggest that reducing caspase-9 activity is a valid therapeutic approach to treating human dementias.

Polymeric drugs: Advances in the development of pharmacologically active polymers

PubMed Central

Li, Jing; Yu, Fei; Chen, Yi; Oupický, David

2015-01-01

Synthetic polymers play a critical role in pharmaceutical discovery and development. Current research and applications of pharmaceutical polymers are mainly focused on their functions as excipients and inert carriers of other pharmacologically active agents. This review article surveys recent advances in alternative pharmaceutical use of polymers as pharmacologically active agents known as polymeric drugs. Emphasis is placed on the benefits of polymeric drugs that are associated with their macromolecular character and their ability to explore biologically relevant multivalency processes. We discuss the main therapeutic uses of polymeric drugs as sequestrants, antimicrobials, antivirals, and anticancer and anti-inflammatory agents. PMID:26410809

Sustained gastrointestinal activity of dendronized polymer-enzyme conjugates

NASA Astrophysics Data System (ADS)

Fuhrmann, Gregor; Grotzky, Andrea; Lukić, Ružica; Matoori, Simon; Luciani, Paola; Yu, Hao; Zhang, Baozhong; Walde, Peter; Schlüter, A. Dieter; Gauthier, Marc A.; Leroux, Jean-Christophe

2013-07-01

Methods to stabilize and retain enzyme activity in the gastrointestinal tract are investigated rarely because of the difficulty of protecting proteins from an environment that has evolved to promote their digestion. Preventing the degradation of enzymes under these conditions, however, is critical for the development of new protein-based oral therapies. Here we show that covalent conjugation to polymers can stabilize orally administered therapeutic enzymes at different locations in the gastrointestinal tract. Architecturally and functionally diverse polymers are used to protect enzymes sterically from inactivation and to promote interactions with mucin on the stomach wall. Using this approach the in vivo activity of enzymes can be sustained for several hours in the stomach and/or in the small intestine. These findings provide new insight and a firm basis for the development of new therapeutic and imaging strategies based on orally administered proteins using a simple and accessible technology.

Protein-Polymer Conjugates: Synthetic Approaches by Controlled Radical Polymerizations & Interesting Applications

PubMed Central

Grover, Gregory N.; Maynard, Heather D.

2011-01-01

Protein-polymer conjugates are of interest to researchers in diverse fields. Attachment of polymers to proteins results in improved pharmacokinetics, which is important in medicine. From an engineering standpoint, conjugates are exciting because they exhibit properties of both the biomolecules and synthetic polymers. This allows the activity of the protein to be altered or tuned, a key aspect in therapeutic design, anchoring conjugates to surfaces, and utilizing these materials for supramolecular self-assembly. Thus, there is broad interest in straightforward synthetic methods to make protein-polymer conjugates. Controlled radical polymerization (CRP) techniques have emerged as excellent strategies to make conjugates because the resulting polymers have narrow molecular weight distributions, targeted molecular weights, and attach to specific sites on proteins. Herein, recent advances in the synthesis and application of protein-polymer conjugates by CRP are highlighted. PMID:21071260

Use of the shape memory polymer polystyrene in the creation of thin film stretchable sensors for wearable applications

NASA Astrophysics Data System (ADS)

Van Volkinburg, Kyle R.; Nguyen, Thao; Pegan, Jonathan D.; Khine, Michelle; Washington, Gregory N.

2016-04-01

The shape memory polymer polystyrene (PS) has been used to create complex hierarchical wrinkling in the fabrication of stretchable thin film bimetallic sensors ideal for wearable based gesture monitoring applications. The film has been bonded to the elastomer polydimethylsiloxane (PDMS) and operates as a strain gauge under the general notion of geometric piezoresistivity. The film was subject to tensile, cyclic, and step loading conditions in order to characterize its dynamic behavior. To measure the joint angle of the metacarpophalangeal (MCP) joint on the right index finger, the sensor was adhered to a fitted golf glove above said joint and a motion study was conducted. At maximum joint angle the sensor experienced roughly 23.5% strain. From the study it was found that two simple curves, one while the finger was in flexion and the other while the finger was in extension, were able to predict the joint angle from measured voltage with an average error of 2.99 degrees.

Stretchable degradable and electroactive shape memory copolymers with tunable recovery temperature enhance myogenic differentiation.

PubMed

Deng, Zexing; Guo, Yi; Zhao, Xin; Li, Longchao; Dong, Ruonan; Guo, Baolin; Ma, Peter X

2016-12-01

Development of flexible degradable electroactive shape memory polymers (ESMPs) with tunable switching temperature (around body temperature) for tissue engineering is still a challenge. Here we designed and synthesized a series of shape memory copolymers with electroactivity, super stretchability and tunable recovery temperature based on poly(ε-caprolactone) (PCL) with different molecular weight and conductive amino capped aniline trimer, and demonstrated their potential to enhance myogenic differentiation from C2C12 myoblast cells. We characterized the copolymers by Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance ( 1 H NMR), cyclic voltammetry (CV), ultraviolet-visible spectroscopy (UV-vis), differential scanning calorimetry (DSC), shape memory test, tensile test and in vitro enzymatic degradation study. The electroactive biodegradable shape memory copolymers showed great elasticity, tunable recovery temperature around 37°C, and good shape memory properties. Furthermore, proliferation and differentiation of C2C12 myoblasts were investigated on electroactive copolymers films, and they greatly enhanced the proliferation, myotube formation and related myogenic differentiation genes expression of C2C12 myoblasts compared to the pure PCL with molecular weight of 80,000. Our study suggests that these electroactive, highly stretchable, biodegradable shape memory polymers with tunable recovery temperature near the body temperature have great potential in skeletal muscle tissue engineering application. Conducting polymers can regulate cell behavior such cell adhesion, proliferation, and differentiation with or without electrical stimulation. Therefore, they have great potential for electrical signal sensitive tissue regeneration. Although conducting biomaterials with degradability have been developed, highly stretchable and electroactive degradable copolymers for soft tissue engineering have been rarely reported. On the other hand, shape

Chronic fluoxetine dissociates contextual from auditory fear memory.

PubMed

Sanders, Jeff; Mayford, Mark

2016-10-06

Fluoxetine is a medication used to treat Major Depressive Disorder and other psychiatric conditions. These experiments studied the effects of chronic fluoxetine treatment on the contextual versus auditory fear memory of mice. We found that chronic fluoxetine treatment of adult mice impaired their contextual fear memory, but spared auditory fear memory. Hippocampal perineuronal nets, which are involved in contextual fear memory plasticity, were unaltered by fluoxetine treatment. These data point to a selective inability to form contextual fear memory as a result of fluoxetine treatment, and they suggest that a blunting of hippocampal-mediated aversive memory may be a therapeutic action for this medication. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Effects of programming and healing temperatures on the healing efficiency of a confined healable polymer composite

NASA Astrophysics Data System (ADS)

Yougoubare, Y. Quentin; Pang, Su-Seng

2014-02-01

In previous work, a biomimetic close-then-heal (CTH) healing mechanism was proposed and validated to repeatedly heal wide-open cracks in load carrying engineering structures by using constrained expansion of compression programmed thermoset shape memory polymers (SMPs). In this study, the effects on healing efficiencies of variation of temperature during both thermomechanical programming and shape recovery (healing) under three-dimensional (3D) confinement are evaluated. The polymer considered is a polystyrene shape memory polymer with 6% by volume of thermoplastic particle additives (copolyester) dispersed in the matrix. In addition to the programming and healing temperatures, some of the parameters investigated include the flexural strength, crack width and elemental composition at the crack interface. It is observed that while increase of the programming temperature is slightly beneficial to strength recovery, most of the strength recovered and damage repair are strongly dependent on the healing temperature. The best healing efficiency (63%) is achieved by a combination of a programming temperature above the glass transition temperature of the polymer and a healing temperature above the bonding point of the copolyester.

Autophagy Enhances Memory Erasure through Synaptic Destabilization.

PubMed

Shehata, Mohammad; Abdou, Kareem; Choko, Kiriko; Matsuo, Mina; Nishizono, Hirofumi; Inokuchi, Kaoru

2018-04-11

There is substantial interest in memory reconsolidation as a target for the treatment of anxiety disorders, such as post-traumatic stress disorder. However, its applicability is restricted by reconsolidation-resistant boundary conditions that constrain the initial memory destabilization. In this study, we investigated whether the induction of synaptic protein degradation through autophagy modulation, a major protein degradation pathway, can enhance memory destabilization upon retrieval and whether it can be used to overcome these conditions. Here, using male mice in an auditory fear reconsolidation model, we showed that autophagy contributes to memory destabilization and its induction can be used to enhance erasure of a reconsolidation-resistant auditory fear memory that depended on AMPAR endocytosis. Using male mice in a contextual fear reconsolidation model, autophagy induction in the amygdala or in the hippocampus enhanced fear or contextual memory destabilization, respectively. The latter correlated with AMPAR degradation in the spines of the contextual memory-ensemble cells. Using male rats in an in vivo LTP reconsolidation model, autophagy induction enhanced synaptic destabilization in an NMDAR-dependent manner. These data indicate that induction of synaptic protein degradation can enhance both synaptic and memory destabilization upon reactivation and that autophagy inducers have the potential to be used as a therapeutic tool in the treatment of anxiety disorders. SIGNIFICANCE STATEMENT It has been reported that inhibiting synaptic protein degradation prevents memory destabilization. However, whether the reverse relation is true and whether it can be used to enhance memory destabilization are still unknown. Here we addressed this question on the behavioral, molecular, and synaptic levels, and showed that induction of autophagy, a major protein degradation pathway, can enhance memory and synaptic destabilization upon reactivation. We also show that autophagy

Long-Term Delivery of Protein Therapeutics

PubMed Central

Vaishya, Ravi; Khurana, Varun; Patel, Sulabh; Mitra, Ashim K

2015-01-01

Introduction Proteins are effective biotherapetics with applications in diverse ailments. Despite being specific and potent, their full clinical potential has not yet been realized. This can be attributed to short half-lives, complex structures, poor in vivo stability, low permeability frequent parenteral administrations and poor adherence to treatment in chronic diseases. A sustained release system, providing controlled release of proteins, may overcome many of these limitations. Areas covered This review focuses on recent development in approaches, especially polymer-based formulations, which can provide therapeutic levels of proteins over extended periods. Advances in particulate, gel based formulations and novel approaches for extended protein delivery are discussed. Emphasis is placed on dosage form, method of preparation, mechanism of release and stability of biotherapeutics. Expert opinion Substantial advancements have been made in the field of extended protein delivery via various polymer-based formulations over last decade despite the unique delivery-related challenges posed by protein biologics. A number of injectable sustained-release formulations have reached market. However, therapeutic application of proteins is still hampered by delivery related issues. A large number of protein molecules are under clinical trials and hence there is an urgent need to develop new methods to deliver these highly potent biologics. PMID:25251334

Epigenetic memory: the Lamarckian brain

PubMed Central

Fischer, Andre

2014-01-01

Recent data support the view that epigenetic processes play a role in memory consolidation and help to transmit acquired memories even across generations in a Lamarckian manner. Drugs that target the epigenetic machinery were found to enhance memory function in rodents and ameliorate disease phenotypes in models for brain diseases such as Alzheimer's disease, Chorea Huntington, Depression or Schizophrenia. In this review, I will give an overview on the current knowledge of epigenetic processes in memory function and brain disease with a focus on Morbus Alzheimer as the most common neurodegenerative disease. I will address the question whether an epigenetic therapy could indeed be a suitable therapeutic avenue to treat brain diseases and discuss the necessary steps that should help to take neuroepigenetic research to the next level. PMID:24719207

Two-way shape memory behavior of semi-crystalline elastomer under stress-free condition

NASA Astrophysics Data System (ADS)

Qian, Chen; Dong, Yubing; Zhu, Yaofeng; Fu, Yaqin

2016-08-01

Semi-crystalline shape memory polymers exhibit two-way shape memory effect (2W-SME) under constant stresses through crystallization-induced elongation upon cooling and melting-induced constriction upon heating. The applied constant stress influenced the prediction and usability of 2W-SME in practical applications without any external force. Here the reversible shape transition in EVA-shaped memory polymer was quantitative analyzed under a suitable temperature range and external stress-free condition. The fraction of reversible strain increased with increasing upper temperature (T high) within the temperature range and reached the maximum value of 13.62% at 70 °C. However, reversible strain transition was almost lost when T high exceeded 80 °C because of complete melting of crystalline scaffold, known as the latent recrystallization template. The non-isothermal annealing of EVA 2W-SMP under changing circulating temperatures was confirmed. Moreover, the orientation of crystallization was retained at high temperatures. These findings may contribute to design an appropriate shape memory protocol based on application-specific requirements.

Catechol polymers for pH-responsive, targeted drug delivery to cancer cells.

PubMed

Su, Jing; Chen, Feng; Cryns, Vincent L; Messersmith, Phillip B

2011-08-10

A novel cell-targeting, pH-sensitive polymeric carrier was employed in this study for delivery of the anticancer drug bortezomib (BTZ) to cancer cells. Our strategy is based on facile conjugation of BTZ to catechol-containing polymeric carriers that are designed to be taken up selectively by cancer cells through cell surface receptor-mediated mechanisms. The polymer used as a building block in this study was poly(ethylene glycol), which was chosen for its ability to reduce nonspecific interactions with proteins and cells. The catechol moiety was exploited for its ability to bind and release borate-containing therapeutics such as BTZ in a pH-dependent manner. In acidic environments, such as in cancer tissue or the subcellular endosome, BTZ dissociates from the polymer-bound catechol groups to liberate the free drug, which inhibits proteasome function. A cancer-cell-targeting ligand, biotin, was presented on the polymer carriers to facilitate targeted entry of drug-loaded polymer carriers into cancer cells. Our study demonstrated that the cancer-targeting drug-polymer conjugates dramatically enhanced cellular uptake, proteasome inhibition, and cytotoxicity toward breast carcinoma cells in comparison with nontargeting drug-polymer conjugates. The pH-sensitive catechol-boronate binding mechanism provides a chemoselective approach for controlling the release of BTZ in targeted cancer cells, establishing a concept that may be applied in the future toward other boronic acid-containing therapeutics to treat a broad range of diseases. © 2011 American Chemical Society

Development of a smart, anti-water polyurethane polymer hair coating for style setting.

PubMed

Liu, Y; Liu, Y J; Hu, J; Ji, F L; Lv, J; Chen, S J; Zhu, Y

2016-06-01

The goal of this work was to develop a novel polyurethane polymer coating for the surface of the hair that could be used for style setting via the shape memory effect (SME). The features of the films are in accordance with conventional hair styling methods used in the laboratory. In this study, a new polyurethane polymer was synthesized; the morphology and mechanical behaviour of the coated hair were systematically investigated using a scanning electron microscope (SEM) and an Instron 5566 (with a temperature oven). The SME of the hair was tested using a 35-g weight and over five washing and drying cycles. The experimental result shows that the polyurethane polymer has effects on the mechanical behaviour of the hair. It indicates that the fixed shape (at 22°C) and recover rate (at 60°C) of different casted thickness films are similar. And the stress of the film becomes larger with increasing film thickness. Furthermore, the shape memory ability could be endowed with the hair styling using this polymer; the hair fibre could recover to the 65% of its original shape after five cycle deformation by 35 g mass under the heat-treated condition; it could recover its original setting styling even after 5th water washing and drying. The SEM results indicated that the microsurface of the hair is coated with the polymer membrane; it contributes to the shape memory ability of the coated hair to keep and recover to the original setting styling. The styling hair can return to the original hair because the polyurethane polymer can be washed out by water with suitable strength and shampoo totally which does not leave any flake. The polyurethane polymer-based hair setting agent has been developed successfully, and it could be coated evenly on the human hair with good hand feeling and SMEs. The SME is highly related to the quantity of polyurethane polymer solution, and the effect could be improved by increasing the solution quantity. The maximum deformation of the coated hair could

Molecular weight (hydrodynamic volume) dictates the systemic pharmacokinetics and tumour disposition of PolyPEG star polymers.

PubMed

Khor, Song Yang; Hu, Jinming; McLeod, Victoria M; Quinn, John F; Williamson, Mark; Porter, Christopher J H; Whittaker, Michael R; Kaminskas, Lisa M; Davis, Thomas P

2015-11-01

Herein we report for the first time the biological fate of poly[(oligoethylene glycol) acrylate] (POEGA) star polymers synthesised via a versatile arm-first reversible addition-fragmentation chain transfer (RAFT) polymerisation approach. The biopharmaceutical behaviour of three different molecular weight (49, 64 and 94kDa) POEGA stars was evaluated in rats and nude mice bearing human MDA MB-231 tumours after intravenous administration. The 94kDa star polymer exhibited a longer plasma exposure time than the 49kDa or 64kDa star polymer; an observation attributable to differences in the rates of both polymer biodegradation and urinary excretion. Tumour biodistribution also correlated with molecular weight and was greatest for the longest circulating 94kDa star. Different patterns of liver and spleen biodistribution were observed between mice and rats for the different sized polymers. The polymers were also well-tolerated in vivo and in vitro at therapeutic concentrations. Advances in nanotechnology has enabled scientists to produce nanoparticle as drug carriers in cancer therapeutics. In this article, the authors studied the biological fate of poly[(oligoethylene glycol) acrylate] (POEGA) star polymers of different size, after intravenous injections. This would allow the subsequent comparison to other drug delivery systems for better drug delivery. Copyright © 2015 Elsevier Inc. All rights reserved.

Reminder duration determines threat memory modification in humans.

PubMed

Hu, Jingchu; Wang, Wenqing; Homan, Philipp; Wang, Penggui; Zheng, Xifu; Schiller, Daniela

2018-06-11

Memory reminders can return a memory into an unstable state such that it will decay unless actively restabilized into long-term memory through reconsolidation. Exposure to a memory reminder, however, does not always lead to destabilization. The 'trace dominance' principle posits that the extent of exposure to memory reminders governs memory susceptibility to disruption. Here, we provide a first systematic investigation of reminder duration effects on threat memory modification in humans. Reminder duration was parametrically varied across 155 participants in a three-day protocol. We found that short reminders (1 s and 4 s) made the memory prone to interference from post-retrieval extinction, suggesting that the memory had been updated. In contrast, no reminder or long reminders (30 s and 3 min) made the memory resistant to such interference, and robustly return. Reminder duration therefore influences memory stability and may be a critical determinant of therapeutic efficacy.

Characterizing and modeling the free recovery and constrained recovery behavior of a polyurethane shape memory polymer

PubMed Central

Volk, Brent L; Lagoudas, Dimitris C; Maitland, Duncan J

2011-01-01

In this work, tensile tests and one-dimensional constitutive modeling are performed on a high recovery force polyurethane shape memory polymer that is being considered for biomedical applications. The tensile tests investigate the free recovery (zero load) response as well as the constrained displacement recovery (stress recovery) response at extension values up to 25%, and two consecutive cycles are performed during each test. The material is observed to recover 100% of the applied deformation when heated at zero load in the second thermomechanical cycle, and a stress recovery of 1.5 MPa to 4.2 MPa is observed for the constrained displacement recovery experiments. After performing the experiments, the Chen and Lagoudas model is used to simulate and predict the experimental results. The material properties used in the constitutive model – namely the coefficients of thermal expansion, shear moduli, and frozen volume fraction – are calibrated from a single 10% extension free recovery experiment. The model is then used to predict the material response for the remaining free recovery and constrained displacement recovery experiments. The model predictions match well with the experimental data. PMID:22003272

High-Temperature Shape Memory Behavior of Semicrystalline Polyamide Thermosets.

PubMed

Li, Ming; Guan, Qingbao; Dingemans, Theo J

2018-05-21

We have explored semicrystalline poly(decamethylene terephthalamide) (PA 10T) based thermosets as single-component high-temperature (>200 °C) shape memory polymers (SMPs). The PA 10T thermosets were prepared from reactive thermoplastic precursors. Reactive phenylethynyl (PE) functionalities were either attached at the chain termini or placed as side groups along the polymer main chain. The shape fixation and recovery performance of the thermoset films were investigated using a rheometer in torsion mode. By controlling the M n of the reactive oligomers, or the PE concentration of the PE side-group functionalized copolyamides, we were able to design dual-shape memory PA 10T thermosets with a broad recovery temperature range of 227-285 °C. The thermosets based on the 1000 g mol -1 reactive PE precursor and the copolyamide with 15 mol % PE side groups show the highest fixation rate (99%) and recovery rate (≥90%). High temperature triple-shape memory behavior can be achieved as well when we use the melt transition ( T m ≥ 200 °C) and the glass transition ( T g = ∼125 °C) as the two switches. The recovery rate of the two recovery steps are highly dependent on the crystallinity of the thermosets and vary within a wide range of 74%-139% and 40-82% for the two steps, respectively. Reversible shape memory events could also be demonstrated when we perform a forward and backward deformation in a triple shape memory cycle. We also studied the angular recovery velocity as a function of temperature, which provides a thermokinematic picture of the shape recovery process and helps to program for desired shape memory behavior.

High-Temperature Shape Memory Behavior of Semicrystalline Polyamide Thermosets

PubMed Central

2018-01-01

We have explored semicrystalline poly(decamethylene terephthalamide) (PA 10T) based thermosets as single-component high-temperature (>200 °C) shape memory polymers (SMPs). The PA 10T thermosets were prepared from reactive thermoplastic precursors. Reactive phenylethynyl (PE) functionalities were either attached at the chain termini or placed as side groups along the polymer main chain. The shape fixation and recovery performance of the thermoset films were investigated using a rheometer in torsion mode. By controlling the Mn of the reactive oligomers, or the PE concentration of the PE side-group functionalized copolyamides, we were able to design dual-shape memory PA 10T thermosets with a broad recovery temperature range of 227–285 °C. The thermosets based on the 1000 g mol–1 reactive PE precursor and the copolyamide with 15 mol % PE side groups show the highest fixation rate (99%) and recovery rate (≥90%). High temperature triple-shape memory behavior can be achieved as well when we use the melt transition (Tm ≥ 200 °C) and the glass transition (Tg = ∼125 °C) as the two switches. The recovery rate of the two recovery steps are highly dependent on the crystallinity of the thermosets and vary within a wide range of 74%–139% and 40–82% for the two steps, respectively. Reversible shape memory events could also be demonstrated when we perform a forward and backward deformation in a triple shape memory cycle. We also studied the angular recovery velocity as a function of temperature, which provides a thermokinematic picture of the shape recovery process and helps to program for desired shape memory behavior. PMID:29742899

Injectable nanoengineered stimuli-responsive hydrogels for on-demand and localized therapeutic delivery.

PubMed

Jalili, Nima A; Jaiswal, Manish K; Peak, Charles W; Cross, Lauren M; Gaharwar, Akhilesh K

2017-10-19

"Smart" hydrogels are an emerging class of biomaterials that respond to external stimuli and have been investigated for a range of biomedical applications, including therapeutic delivery and regenerative engineering. Stimuli-responsive nanogels constructed of thermoresponsive polymers such as poly(N-isopropylacrylamide-co-acrylamide) (poly(NIPAM-co-AM)) and magnetic nanoparticles (MNPs) have been developed as "smart carriers" for on-demand delivery of therapeutic biomolecules via magneto-thermal activation. However, due to their small size and systemic introduction, these poly(NIPAM-co-AM)/MNP nanogels result in limited control over long-term, localized therapeutic delivery. Here, we developed an injectable nanoengineered hydrogel loaded with poly(NIPAM-co-AM)/MNPs for localized, on-demand delivery of therapeutics (doxorubicin (DOX)). We have engineered shear-thinning and self-recoverable hydrogels by modulating the crosslinking density of a gelatin methacrylate (GelMA) network. Poly(NIPAM-co-AM)/MNP nanogels loaded with DOX were entrapped within a GelMA pre-polymer solution prior to crosslinking. The temperature and magnetic field dependent release of loaded DOX was observed from the nanoengineered hydrogels (GelMA/(poly(NIPAM-co-AM)/MNPs)). Finally, the in vitro efficacy of DOX released from injectable nanoengineered hydrogels was investigated using preosteoblast and osteosarcoma cells. Overall, these results demonstrated that the injectable nanoengineered hydrogels could be used for on-demand and localized therapeutic delivery for biomedical applications.

Lipid-polymer hybrid nanoparticles as a new generation therapeutic delivery platform: a review.

PubMed

Hadinoto, Kunn; Sundaresan, Ajitha; Cheow, Wean Sin

2013-11-01

Lipid-polymer hybrid nanoparticles (LPNs) are core-shell nanoparticle structures comprising polymer cores and lipid/lipid-PEG shells, which exhibit complementary characteristics of both polymeric nanoparticles and liposomes, particularly in terms of their physical stability and biocompatibility. Significantly, the LPNs have recently been demonstrated to exhibit superior in vivo cellular delivery efficacy compared to that obtained from polymeric nanoparticles and liposomes. Since their inception, the LPNs have advanced significantly in terms of their preparation strategy and scope of applications. Their preparation strategy has undergone a shift from the conceptually simple two-step method, involving preformed polymeric nanoparticles and lipid vesicles, to the more principally complex, yet easier to perform, one-step method, relying on simultaneous self-assembly of the lipid and polymer, which has resulted in better products and higher production throughput. The scope of LPNs' applications has also been extended beyond single drug delivery for anticancer therapy, to include combinatorial and active targeted drug deliveries, and deliveries of genetic materials, vaccines, and diagnostic imaging agents. This review details the current state of development for the LPNs preparation and applications from which we identify future research works needed to bring the LPNs closer to its clinical realization. Copyright © 2013 Elsevier B.V. All rights reserved.

Understanding Graphics on a Scalable Latching Assistive Haptic Display Using a Shape Memory Polymer Membrane.

PubMed

Besse, Nadine; Rosset, Samuel; Zarate, Juan Jose; Ferrari, Elisabetta; Brayda, Luca; Shea, Herbert

2018-01-01

We present a fully latching and scalable 4 × 4 haptic display with 4 mm pitch, 5 s refresh time, 400 mN holding force, and 650 μm displacement per taxel. The display serves to convey dynamic graphical information to blind and visually impaired users. Combining significant holding force with high taxel density and large amplitude motion in a very compact overall form factor was made possible by exploiting the reversible, fast, hundred-fold change in the stiffness of a thin shape memory polymer (SMP) membrane when heated above its glass transition temperature. Local heating is produced using an addressable array of 3 mm in diameter stretchable microheaters patterned on the SMP. Each taxel is selectively and independently actuated by synchronizing the local Joule heating with a single pressure supply. Switching off the heating locks each taxel into its position (up or down), enabling holding any array configuration with zero power consumption. A 3D-printed pin array is mounted over the SMP membrane, providing the user with a smooth and room temperature array of movable pins to explore by touch. Perception tests were carried out with 24 blind users resulting in 70 percent correct pattern recognition over a 12-word tactile dictionary.

The effect of moisture absorption on the physical properties of polyurethane shape memory polymer foams.

PubMed

Yu, Ya-Jen; Hearon, Keith; Wilson, Thomas S; Maitland, Duncan J

2011-08-01

The effect of moisture absorption on the glass transition temperature (T(g)) and stress/strain behavior of network polyurethane shape memory polymer (SMP) foams has been investigated. With our ultimate goal of engineering polyurethane SMP foams for use in blood contacting environments, we have investigated the effects of moisture exposure on the physical properties of polyurethane foams. To our best knowledge, this study is the first to investigate the effects of moisture absorption at varying humidity levels (non-immersion and immersion) on the physical properties of polyurethane SMP foams. The SMP foams were exposed to differing humidity levels for varying lengths of time, and they exhibited a maximum water uptake of 8.0% (by mass) after exposure to 100% relative humidity for 96 h. Differential scanning calorimetry results demonstrated that water absorption significantly decreased the T(g) of the foam, with a maximum water uptake shifting the T(g) from 67 °C to 5 °C. Samples that were immersed in water for 96 h and immediately subjected to tensile testing exhibited 100% increases in failure strains and 500% decreases in failure stresses; however, in all cases of time and humidity exposure, the plasticization effect was reversible upon placing moisture-saturated samples in 40% humidity environments for 24 h.

The effect of moisture absorption on the physical properties of polyurethane shape memory polymer foams

PubMed Central

Yu, Ya-Jen; Hearon, Keith; Wilson, Thomas S.; Maitland, Duncan J.

2011-01-01

The effect of moisture absorption on the glass transition temperature (Tg) and stress/strain behavior of network polyurethane shape memory polymer (SMP) foams has been investigated. With our ultimate goal of engineering polyurethane SMP foams for use in blood contacting environments, we have investigated the effects of moisture exposure on the physical properties of polyurethane foams. To our best knowledge, this study is the first to investigate the effects of moisture absorption at varying humidity levels (non-immersion and immersion) on the physical properties of polyurethane SMP foams. The SMP foams were exposed to differing humidity levels for varying lengths of time, and they exhibited a maximum water uptake of 8.0% (by mass) after exposure to 100% relative humidity for 96 h. Differential scanning calorimetry results demonstrated that water absorption significantly decreased the Tg of the foam, with a maximum water uptake shifting the Tg from 67 °C to 5 °C. Samples that were immersed in water for 96 h and immediately subjected to tensile testing exhibited 100% increases in failure strains and 500% decreases in failure stresses; however, in all cases of time and humidity exposure, the plasticization effect was reversible upon placing moisture-saturated samples in 40% humidity environments for 24 h. PMID:21949469

The effect of moisture absorption on the physical properties of polyurethane shape memory polymer foams

NASA Astrophysics Data System (ADS)

Yu, Ya-Jen; Hearon, Keith; Wilson, Thomas S.; Maitland, Duncan J.

2011-08-01

The effect of moisture absorption on the glass transition temperature (Tg) and the stress/strain behavior of network polyurethane shape memory polymer (SMP) foams has been investigated. With our ultimate goal of engineering polyurethane SMP foams for use in blood-contacting environments, we have investigated the effects of moisture exposure on the physical properties of polyurethane foams. To the best of our knowledge, this study is the first to investigate the effects of moisture absorption at varying humidity levels (non-immersion and immersion) on the physical properties of polyurethane SMP foams. The SMP foams were exposed to differing humidity levels for varying lengths of time, and they exhibited a maximum water uptake of 8.0% (by mass) after exposure to 100% relative humidity for 96 h. Differential scanning calorimetry results demonstrated that water absorption significantly decreased the Tg of the foam, with a maximum water uptake shifting the Tg from 67 to 5 °C. Samples that were immersed in water for 96 h and immediately subjected to tensile testing exhibited 100% increases in failure strains and 500% decreases in failure stresses; however, in all cases of time and humidity exposure, the plasticization effect was reversible upon placing moisture-saturated samples in 40% humidity environments for 24 h.

Laser Fabrication of Polymer Ferroelectric Nanostructures for Nonvolatile Organic Memory Devices.

PubMed

Martínez-Tong, Daniel E; Rodríguez-Rodríguez, Álvaro; Nogales, Aurora; García-Gutiérrez, Mari-Cruz; Pérez-Murano, Francesc; Llobet, Jordi; Ezquerra, Tiberio A; Rebollar, Esther

2015-09-09

Polymer ferroelectric laser-induced periodic surface structures (LIPSS) have been prepared on ferroelectric thin films of a poly(vinylidene fluoride-trifluoroethylene) copolymer. Although this copolymer does not absorb light at the laser wavelength, LIPSS on the copolymer can be obtained by forming a bilayer with other light-absorbing polymers. The ferroelectric nature of the structured bilayer was proven by piezoresponse force microscopy measurements. Ferroelectric hysteresis was found on both the bilayer and the laser-structured bilayer. We show that it is possible to write ferroelectric information at the nanoscale. The laser-structured ferroelectric bilayer showed an increase in the information storage density of an order of magnitude, in comparison to the original bilayer.

Affect and the therapeutic action of psychoanalysis.

PubMed

Andrade, Victor Manoel

2005-06-01

In connection with controversial IJP articles by Stern et al. and Fonagy on the interpretation of the repressed and the recovery of past memories, the author maintains that the affect that is inherent in positive transference is at the heart of therapeutic action. Points of view put forward in the controversy (based on neurobiological knowledge) are related to Freudian metapsychology, as well as to their precursors whose scope was necessarily limited by a lack of access to more recent scientific discoveries. The author demonstrates metapsychological elements of therapeutic action inherent in the intersubjective relationship, especially identification, manifested in introjection and empathy. He describes cognitive development as spontaneously blossoming from the affective nucleus, and he explains the neuroscientific bases of this step forward. The classic (interpretative) psychoanalytic method makes up the cognitive superstructure necessary for the organisation of the mind that has sprung from the affective substructure. As a primary factor in psychic change, interpretation is limited in effectiveness to pathologies arising from the verbal phase, related to explicit memories, with no effect in the pre-verbal phase where implicit memories are to be found. Interpretation--the method used to the exclusion of all others for a century--is only partial; when used in isolation it does not meet the demands of modern broad-spectrum psychoanalysis, as the clinical material presented illustrates.

Caspase-9 mediates synaptic plasticity and memory deficits of Danish dementia knock-in mice: caspase-9 inhibition provides therapeutic protection

PubMed Central

2012-01-01

Background Mutations in either Aβ Precursor protein (APP) or genes that regulate APP processing, such as BRI2/ITM2B and PSEN1/PSEN2, cause familial dementias. Although dementias due to APP/PSEN1/PSEN2 mutations are classified as familial Alzheimer disease (FAD) and those due to mutations in BRI2/ITM2B as British and Danish dementias (FBD, FDD), data suggest that these diseases have a common pathogenesis involving toxic APP metabolites. It was previously shown that FAD mutations in APP and PSENs promote activation of caspases leading to the hypothesis that aberrant caspase activation could participate in AD pathogenesis. Results Here, we tested whether a similar mechanism applies to the Danish BRI2/ITM2B mutation. We have generated a genetically congruous mouse model of FDD, called FDDKI, which presents memory and synaptic plasticity deficits. We found that caspase-9 is activated in hippocampal synaptic fractions of FDDKI mice and inhibition of caspase-9 activity rescues both synaptic plasticity and memory deficits. Conclusion These data directly implicate caspase-9 in the pathogenesis of Danish dementia and suggest that reducing caspase-9 activity is a valid therapeutic approach to treating human dementias. PMID:23217200

High-strain slide-ring shape-memory polycaprolactone-based polyurethane.

PubMed

Wu, Ruiqing; Lai, Jingjuan; Pan, Yi; Zheng, Zhaohui; Ding, Xiaobin

2018-06-06

To enable shape-memory polymer networks to achieve recoverable high deformability with a simultaneous high shape-fixity ratio and shape-recovery ratio, novel semi-crystalline slide-ring shape-memory polycaprolactone-based polyurethane (SR-SMPCLU) with movable net-points constructed by a topologically interlocked slide-ring structure was designed and fabricated. The SR-SMPCLU not only exhibited good shape fixity, almost complete shape recovery, and a fast shape-recovery speed, it also showed an outstanding recoverable high-strain capacity with 95.83% Rr under a deformation strain of 1410% due to the pulley effect of the topological slide-ring structure. Furthermore, the SR-SMPCLU system maintained excellent shape-memory performance with increasing the training cycle numbers at 45% and even 280% deformation strain. The effects of the slide-ring cross-linker content, deformation strain, and successive shape-memory cycles on the shape-memory performance were investigated. A possible mechanism for the shape-memory effect of the SR-SMPCLU system is proposed.

High Cycle-life Shape Memory Polymer at High Temperature

PubMed Central

Kong, Deyan; Xiao, Xinli

2016-01-01

High cycle-life is important for shape memory materials exposed to numerous cycles, and here we report shape memory polyimide that maintained both high shape fixity (Rf) and shape recovery (Rr) during the more than 1000 bending cycles tested. Its critical stress is 2.78 MPa at 250 °C, and the shape recovery process can produce stored energy of 0.218 J g−1 at the efficiency of 31.3%. Its high Rf is determined by the large difference in storage modulus at rubbery and glassy states, while the high Rr mainly originates from its permanent phase composed of strong π-π interactions and massive chain entanglements. Both difference in storage modulus and overall permanent phase were preserved during the bending deformation cycles, and thus high Rf and Rr were observed in every cycle and the high cycle-life will expand application areas of SMPs enormously. PMID:27641148

Design of Stomach Acid-Stable and Mucin-Binding Enzyme Polymer Conjugates.

PubMed

Cummings, Chad S; Campbell, Alan S; Baker, Stefanie L; Carmali, Sheiliza; Murata, Hironobu; Russell, Alan J

2017-02-13

The reduced immunogenicity and increased stability of protein-polymer conjugates has made their use in therapeutic applications particularly attractive. However, the physicochemical interactions between polymer and protein, as well as the effect of this interaction on protein activity and stability, are still not fully understood. In this work, polymer-based protein engineering was used to examine the role of polymer physicochemical properties on the activity and stability of the chymotrypsin-polymer conjugates and their degree of binding to intestinal mucin. Four different chymotrypsin-polymer conjugates, each with the same polymer density, were synthesized using "grafting-from" atom transfer radical polymerization. The influence of polymer charge on chymotrypsin-polymer conjugate mucin binding, bioactivity, and stability in stomach acid was determined. Cationic polymers covalently attached to chymotrypsin showed high mucin binding, while zwitterionic, uncharged, and anionic polymers showed no mucin binding. Cationic polymers also increased chymotrypsin activity from pH 6-8, while zwitterionic polymers had no effect, and uncharged and anionic polymers decreased enzyme activity. Lastly, cationic polymers decreased the tendency of chymotrypsin to structurally unfold at extremely low pH, while uncharged and anionic polymers induced unfolding more quickly. We hypothesized that when polymers are covalently attached to the surface of a protein, the degree to which those polymers interact with the protein surface is the predominant determinant of whether the polymer will stabilize or inactivate the protein. Preferential interactions between the polymer and the protein lead to removal of water from the surface of the protein, and this, we believe, inactivates the enzyme.

Physics of the gut: How polymers dynamically structure the gut environment

NASA Astrophysics Data System (ADS)

Preska Steinberg, Asher; Datta, Sujit; Bogatyrev, Said; Ismagilov, Rustem

While the gut microbiome and biological regulation of the gut environment is being exhaustively studied by the microbiology community, little is known about the rich physics that governs the macro- and microstructure of the gut environment. The mammalian gut abounds in soft materials; ranging from soluble polymers (e.g. dietary fibers, therapeutic polymers and mucins) to colloidal matter (e.g. bacteria, viruses and nanoparticles carrying drugs). We have found experimentally that soluble polymers can dynamically re-structure the colonic mucus hydrogel by modulating its degree of swelling. We implemented a mean-field Flory-Huggins model to reveal that these polymer-mucus interactions can be captured using a simple, first principles thermodynamics model. In this model, the amount of deswelling increases with polymer concentration and size. We then used these physical principles to make predictions about how different polymer solutions affect the structure of mucus. Lastly, we explore applying this framework and similar physical principles to a variety of biological problems in the gut.

Catching the engram: strategies to examine the memory trace

PubMed Central

2012-01-01

Memories are stored within neuronal ensembles in the brain. Modern genetic techniques can be used to not only visualize specific neuronal ensembles that encode memories (e.g., fear, craving) but also to selectively manipulate those neurons. These techniques are now being expanded for the study of various types of memory. In this review, we will summarize the genetic methods used to visualize and manipulate neurons involved in the representation of memory engrams. The methods will help clarify how memory is encoded, stored and processed in the brain. Furthermore, these approaches may contribute to our understanding of the pathological mechanisms associated with human memory disorders and, ultimately, may aid the development of therapeutic strategies to ameliorate these diseases. PMID:22999350

Catching the engram: strategies to examine the memory trace.

PubMed

Sakaguchi, Masanori; Hayashi, Yasunori

2012-09-21

Memories are stored within neuronal ensembles in the brain. Modern genetic techniques can be used to not only visualize specific neuronal ensembles that encode memories (e.g., fear, craving) but also to selectively manipulate those neurons. These techniques are now being expanded for the study of various types of memory. In this review, we will summarize the genetic methods used to visualize and manipulate neurons involved in the representation of memory engrams. The methods will help clarify how memory is encoded, stored and processed in the brain. Furthermore, these approaches may contribute to our understanding of the pathological mechanisms associated with human memory disorders and, ultimately, may aid the development of therapeutic strategies to ameliorate these diseases.

Therapeutic nucleic acids: current clinical status

PubMed Central

Sridharan, Kannan

2016-01-01

Abstract Deoxyribonucleic acid (DNA) and ribonucleic acid (RNA) are simple linear polymers that have been the subject of considerable research in the last two decades and have now moved into the realm of being stand‐alone therapeutic agents. Much of this has stemmed from the appreciation that they carry out myriad functions that go beyond mere storage of genetic information and protein synthesis. Therapy with nucleic acids either uses unmodified DNA or RNA or closely related compounds. From both a development and regulatory perspective, they fall somewhere between small molecules and biologics. Several of these compounds are in clinical development and many have received regulatory approval for human use. This review addresses therapeutic uses of DNA based on antisense oligonucleotides, DNA aptamers and gene therapy; and therapeutic uses of RNA including micro RNAs, short interfering RNAs, ribozymes, RNA decoys and circular RNAs. With their specificity, functional diversity and limited toxicity, therapeutic nucleic acids hold enormous promise. However, challenges that need to be addressed include targeted delivery, mass production at low cost, sustaining efficacy and minimizing off‐target toxicity. Technological developments will hold the key to this and help accelerate drug approvals in the years to come. PMID:27111518

Chemical cross-linking of polypropylenes towards new shape memory polymers.

PubMed

Raidt, Thomas; Hoeher, Robin; Katzenberg, Frank; Tiller, Joerg C

2015-04-01

In this work, syndiotactic polypropylene (sPP) as well as isotactic polypropylene (iPP) are cross-linked to gain a shape memory effect. Both prepared PP networks exhibit maximum strains of 700%, stored strains of up to 680%, and recoveries of nearly 100%. While x-iPP is stable for many cycles, x-sPP ruptures after the first shape-memory cycle. It is shown by wide-angle X-ray scattering (WAXS) experiments that cross-linked iPP exhibits homoepitaxy in the temporary, stretched shape but in contrast to previous reports it contains a higher amount of daughter than mother crystals. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Frameworking memory and serotonergic markers.

PubMed

Meneses, Alfredo

2017-07-26

The evidence for neural markers and memory is continuously being revised, and as evidence continues to accumulate, herein, we frame earlier and new evidence. Hence, in this work, the aim is to provide an appropriate conceptual framework of serotonergic markers associated with neural activity and memory. Serotonin (5-hydroxytryptamine [5-HT]) has multiple pharmacological tools, well-characterized downstream signaling in mammals' species, and established 5-HT neural markers showing new insights about memory functions and dysfunctions, including receptors (5-HT1A/1B/1D, 5-HT2A/2B/2C, and 5-HT3-7), transporter (serotonin transporter [SERT]) and volume transmission present in brain areas involved in memory. Bidirectional influence occurs between 5-HT markers and memory/amnesia. A growing number of researchers report that memory, amnesia, or forgetting modifies neural markers. Diverse approaches support the translatability of using neural markers and cerebral functions/dysfunctions, including memory formation and amnesia. At least, 5-HT1A, 5-HT4, 5-HT6, and 5-HT7 receptors and SERT seem to be useful neural markers and therapeutic targets. Hence, several mechanisms cooperate to achieve synaptic plasticity or memory, including changes in the expression of neurotransmitter receptors and transporters.

Episodic Memories in Anxiety Disorders: Clinical Implications

PubMed Central

Zlomuzica, Armin; Dere, Dorothea; Machulska, Alla; Adolph, Dirk; Dere, Ekrem; Margraf, Jürgen

2014-01-01

The aim of this review is to summarize research on the emerging role of episodic memories in the context of anxiety disorders (AD). The available literature on explicit, autobiographical, and episodic memory function in AD including neuroimaging studies is critically discussed. We describe the methodological diversity of episodic memory research in AD and discuss the need for novel tests to measure episodic memory in a clinical setting. We argue that alterations in episodic memory functions might contribute to the etiology of AD. We further explain why future research on the interplay between episodic memory function and emotional disorders as well as its neuroanatomical foundations offers the promise to increase the effectiveness of modern psychological treatments. We conclude that one major task is to develop methods and training programs that might help patients suffering from AD to better understand, interpret, and possibly actively use their episodic memories in a way that would support therapeutic interventions and counteract the occurrence of symptoms. PMID:24795583

A cytokine-delivering polymer is effective in reducing tumor burden in a head and neck squamous cell carcinoma murine model.

PubMed

Lin, Yuan; Luo, Jie; Zhu, Weichao Eric; Srivastava, Minu; Schaue, Dorthe; Elashoff, David A; Dubinett, Steven M; Sharma, Sherven; Wu, Benjamin; St John, Maie A

2014-09-01

This study aimed to evaluate the therapeutic efficacy of a novel polymer platform delivering cisplatin and cytokines in the treatment of head and neck squamous cell carcinoma (HNSCC). In vivo study. Academic research laboratory. Mice were randomized to receive implantation of (1) no polymer, (2) plain polymer, (3) plain polymer with local cisplatin injection, or (4) cisplatin polymer. The 2 groups of mice implanted with cisplatin polymer or no polymer were further randomized to receive (1) 4 Grays external beam radiation for 4 days or (2) no radiation. For cytokine studies, mice were grouped into (1) no polymer, (2) plain polymer, (3) plain polymer with intratumoral injection of recombinant CCL21 twice a week, (4) polymer containing parental dendritic cells, or (5) polymer containing dendritic cells secreting CCL21 (DC-CCL21). The cisplatin-secreting polymer effectively reduced tumors in the mice by more than 16-fold (P < .01). We also observed a statistically significant lower tumor weight among mice treated with cisplatin polymer and concomitant radiation compared to control groups. The DC-CCL21 polymer reduced SCCVII/SF tumors in the C3H/HeJ mice by more than 41% (P < .01). Herein, we demonstrate the efficacy of a novel polymer platform in delivering cisplatin and cytokines. We also demonstrate that we can effectively grow dendritic cells in the polymer that can actively secrete CCL21 for a minimum of 5 days. This polymer may represent a new therapeutic modality for patients with HNSCC. Once this polymer platform is optimized, we will plan to pursue prospective trials in patients with HNSCC. © American Academy of Otolaryngology—Head and Neck Surgery Foundation 2014.

The evolving roles of memory immune cells in transplantation

PubMed Central

Chen, Wenhao; Ghobrial, Rafik M.; Li, Xian C.

2015-01-01

Memory cells are the products of immune responses but also exert significant impact on subsequent immunity and immune tolerance, thus placing them in a unique position in transplant research. Memory cells are heterogeneous, including not only memory T cells but also memory B cells and innate memory cells. Memory cells are a critical component of protective immunity against invading pathogens, especially in immunosuppressed patients, but they also mediate graft loss and tolerance resistance. Recent studies suggest that some memory cells unexpectedly act as regulatory cells, promoting rather than hindering transplant survival. This functional diversity makes therapeutic targeting of memory cells a challenging task in transplantation. In this article we highlight recent advances in our understanding of memory cells, focusing on diversity of memory cells and mechanisms involved in their induction and functions. We also provide a broad overview on the challenges and opportunities in targeting memory cells in the induction of transplant tolerance. PMID:26102615

Biocomputing nanoplatforms as therapeutics and diagnostics.

PubMed

Evans, A C; Thadani, N N; Suh, J

2016-10-28

Biocomputing nanoplatforms are designed to detect and integrate single or multiple inputs under defined algorithms, such as Boolean logic gates, and generate functionally useful outputs, such as delivery of therapeutics or release of optically detectable signals. Using sensing modules composed of small molecules, polymers, nucleic acids, or proteins/peptides, nanoplatforms have been programmed to detect and process extrinsic stimuli, such as magnetic fields or light, or intrinsic stimuli, such as nucleic acids, enzymes, or pH. Stimulus detection can be transduced by the nanomaterial via three different mechanisms: system assembly, system disassembly, or system transformation. The increasingly sophisticated suite of biocomputing nanoplatforms may be invaluable for a multitude of applications, including medical diagnostics, biomedical imaging, environmental monitoring, and delivery of therapeutics to target cell populations. Copyright © 2016 Elsevier B.V. All rights reserved.

Degradability of Polymers for Implantable Biomedical Devices

PubMed Central

Lyu, SuPing; Untereker, Darrel

2009-01-01

Many key components of implantable medical devices are made from polymeric materials. The functions of these materials include structural support, electrical insulation, protection of other materials from the environment of the body, and biocompatibility, as well as other things such as delivery of a therapeutic drug. In such roles, the stability and integrity of the polymer, over what can be a very long period of time, is very important. For most of these functions, stability over time is desired, but in other cases, the opposite–the degradation and disappearance of the polymer over time is required. In either case, it is important to understand both the chemistry that can lead to the degradation of polymers as well as the kinetics that controls these reactions. Hydrolysis and oxidation are the two classes of reactions that lead to the breaking down of polymers. Both are discussed in detail in the context of the environmental factors that impact the utility of various polymers for medical device applications. Understanding the chemistry and kinetics allows prediction of stability as well as explanations for observations such as porosity and the unexpected behavior of polymeric composite materials in some situations. In the last part, physical degradation such interfacial delamination in composites is discussed. PMID:19865531

Synthesis of Biocompatible Nanoparticulate Coordination Polymers for Diagnostic and Therapeutic Applications

NASA Astrophysics Data System (ADS)

Kandanapitiye, Murthi S.

The combination of nanotechnology with medicinal chemistry has developed into a burgeoning research area. Nanomaterials (NMs) could be seamlessly interfaced with various facets in biology, biochemistry, medicinal chemistry and environmental chemistry that may not be available to the same material in the bulk scale. This dissertation research has focused on the development of nanoparticulate coordination polymers for diagnostic and therapeutic applications. Modern imaging techniques include X-ray computed tomography (CT), magnetic resonance imaging (MRI), single photon emission computed tomography (SPECT) and positron emission tomography (PET). We have successfully developed several types of nanoparticulate diagnostics and therapeutics that have some potential usefulness in biomedicine. Synthesis and characterization of nanoparticulate based PET (Positron emission tomography)/SPECT (Single photon emission computed tomography) are discussed in chapter 3. In chapter 4, preparation and potential utility of non-gadolinium based MRI contrast agent are reported for T1-weighted application. As far as the solely effectiveness of relaxation is concerned, Gd-based T 1-weighted MRI contrast agents have excellent enhancement of image contrast but they have risks of biological toxicity. Consequently, the search for T 1-weighted CAs with high efficacy and low toxicity has gained attention toward the Mn(II) and Fe(III). Fe(III) is considered to be more toxic to cells because free ferric or ferrous ions can catalyze the production of reactive oxygen species via the Fenton reactions. Paramagnetic chelates of Mn(II) could be employed as T1-weighted CAs. However, it is challenging to design and synthesize highly stable Mn(II) complexes that could maintain the integrity when administered to living system. Chapter 4 describes the synthesis and utility of nanoparticulate Mn analogue of Prussian blue (K2Mn 3[FeII(CN)6]2) as an effective T1 MRI contrast agent for cellular imaging X

Surface Control of Cold Hibernated Elastic Memory Self-Deployable Structure

NASA Technical Reports Server (NTRS)

Sokolowski, Witold M.; Ghaffarian, Reza

2006-01-01

A new class of simple, reliable, lightweight, low packaging volume and cost, self-deployable structures has been developed for use in space and commercial applications. This technology called 'cold hibernated elastic memory' (CHEM) utilizes shape memory polymers (SMP)in open cellular (foam) structure or sandwich structures made of shape memory polymer foam cores and polymeric composite skins. Some of many potential CHEM space applications require a high precision deployment and surface accuracy during operation. However, a CHEM structure could be slightly distorted by the thermo-mechanical processing as well as by thermal space environment Therefore, the sensor system is desirable to monitor and correct the potential surface imperfection. During these studies, the surface control of CHEM smart structures was demonstrated using a Macro-Fiber Composite (MFC) actuator developed by the NASA LaRC and US Army ARL. The test results indicate that the MFC actuator performed well before and after processing cycles. It reduced some residue compressive strain that in turn corrected very small shape distortion after each processing cycle. The integrated precision strain gages were detecting only a small flat shape imperfection indicating a good recoverability of original shape of the CHEM test structure.

Ion-Conducting Organic/Inorganic Polymers

NASA Technical Reports Server (NTRS)

Kinder, James D.; Meador, Mary Ann B.

2007-01-01

Ion-conducting polymers that are hybrids of organic and inorganic moieties and that are suitable for forming into solid-electrolyte membranes have been invented in an effort to improve upon the polymeric materials that have been used previously for such membranes. Examples of the prior materials include perfluorosulfonic acid-based formulations, polybenzimidazoles, sulfonated polyetherketone, sulfonated naphthalenic polyimides, and polyethylene oxide (PEO)-based formulations. Relative to the prior materials, the polymers of the present invention offer greater dimensional stability, greater ease of formation into mechanically resilient films, and acceptably high ionic conductivities over wider temperature ranges. Devices in which films made of these ion-conducting organic/inorganic polymers could be used include fuel cells, lithium batteries, chemical sensors, electrochemical capacitors, electrochromic windows and display devices, and analog memory devices. The synthesis of a polymer of this type (see Figure 1) starts with a reaction between an epoxide-functionalized alkoxysilane and a diamine. The product of this reaction is polymerized by hydrolysis and condensation of the alkoxysilane group, producing a molecular network that contains both organic and inorganic (silica) links. The silica in the network contributes to the ionic conductivity and to the desired thermal and mechanical properties. Examples of other diamines that have been used in the reaction sequence of Figure 1 are shown in Figure 2. One can use any of these diamines or any combination of them in proportions chosen to impart desired properties to the finished product. Alternatively or in addition, one could similarly vary the functionality of the alkoxysilane to obtain desired properties. The variety of available alkoxysilanes and diamines thus affords flexibility to optimize the organic/inorganic polymer for a given application.

Phase-Change Thermoplastic Elastomer Blends for Tunable Shape Memory by Physical Design

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mineart, Kenneth P.; Tallury, Syamal S.; Li, Tao

Shape-memory polymers (SMPs) change shape upon exposure to an environmental stimulus.1-3 They are of considerable importance in the ongoing development of stimuli-responsive biomedical4,5 and deployable6 devices, and their function depends on the presence of two components.7 The first provides mechanical rigidity to ensure retention of one or more temporary strain states and also serves as a switch capable of releasing a temporary strain state. The second, a network-forming component, is required to restore the polymer to a prior strain state upon stimulation. In thermally-activated SMPs, the switching element typically relies on a melting or glass transition temperature,1-3,7 and broad ormore » multiple switches permit several temporary strain states.8-10 Chemical integration of network-forming and switching species endows SMPs with specific properties.8,10,11 Here, we demonstrate that phase-change materials incorporated into network-forming macromolecules yield shape-memory polymer blends (SMPBs) with physically tunable switching temperatures and recovery kinetics for use in multi-responsive laminates and shape-change electronics.« less

Fabrication and in vitro deployment of a laser-activated shape memory polymer vascular stent

PubMed Central

Baer, Géraldine M; Small, Ward; Wilson, Thomas S; Benett, William J; Matthews, Dennis L; Hartman, Jonathan; Maitland, Duncan J

2007-01-01

Background Vascular stents are small tubular scaffolds used in the treatment of arterial stenosis (narrowing of the vessel). Most vascular stents are metallic and are deployed either by balloon expansion or by self-expansion. A shape memory polymer (SMP) stent may enhance flexibility, compliance, and drug elution compared to its current metallic counterparts. The purpose of this study was to describe the fabrication of a laser-activated SMP stent and demonstrate photothermal expansion of the stent in an in vitro artery model. Methods A novel SMP stent was fabricated from thermoplastic polyurethane. A solid SMP tube formed by dip coating a stainless steel pin was laser-etched to create the mesh pattern of the finished stent. The stent was crimped over a fiber-optic cylindrical light diffuser coupled to an infrared diode laser. Photothermal actuation of the stent was performed in a water-filled mock artery. Results At a physiological flow rate, the stent did not fully expand at the maximum laser power (8.6 W) due to convective cooling. However, under zero flow, simulating the technique of endovascular flow occlusion, complete laser actuation was achieved in the mock artery at a laser power of ~8 W. Conclusion We have shown the design and fabrication of an SMP stent and a means of light delivery for photothermal actuation. Though further studies are required to optimize the device and assess thermal tissue damage, photothermal actuation of the SMP stent was demonstrated. PMID:18042294

Recovery behaviour of shape memory polyurethane based laminates after thermoforming

NASA Astrophysics Data System (ADS)

Wu, Shuiliang; Xu, Wensen; Prasath Balamurugan, G.; Thompson, Michael R.; Nielsen, Kent E.; Brandys, Frank A.

2017-11-01

Shape memory polymers (SMPs) can be used to produce a new class of decorative films capable of improved formability and shape recovery in polymer laminates, which are increasingly being used for automotive, aerospace, construction and commercial applications. As a relatively new field there is little knowledge on the shape recovery behaviour of laminates with a SMP film and few methods of quantify that behaviour. The influences of different variables that affect the recovery behaviour of thermoplastic shape memory polyurethanes based laminates including ambient temperature (45 °C and 65 °C), material modulus, and adhesive strength were investigated after thermoforming, through both experimental and modelling methods. The empirical model assisted in identifying the contributions of the adhesive to transfer stresses, which dampened the recovery of the laminate with lower shear strength adhesives. Increasing ambient temperature and the film modulus increased both the final angle recovery ratios and recovery rates.

Flexible non-volatile memory devices based on organic semiconductors

NASA Astrophysics Data System (ADS)

Cosseddu, Piero; Casula, Giulia; Lai, Stefano; Bonfiglio, Annalisa

2015-09-01

The possibility of developing fully organic electronic circuits is critically dependent on the ability to realize a full set of electronic functionalities based on organic devices. In order to complete the scene, a fundamental element is still missing, i.e. reliable data storage. Over the past few years, a considerable effort has been spent on the development and optimization of organic polymer based memory elements. Among several possible solutions, transistor-based memories and resistive switching-based memories are attracting a great interest in the scientific community. In this paper, a route for the fabrication of organic semiconductor-based memory devices with performances beyond the state of the art is reported. Both the families of organic memories will be considered. A flexible resistive memory based on a novel combination of materials is presented. In particular, high retention time in ambient conditions are reported. Complementary, a low voltage transistor-based memory is presented. Low voltage operation is allowed by an hybrid, nano-sized dielectric, which is also responsible for the memory effect in the device. Thanks to the possibility of reproducibly fabricating such device on ultra-thin substrates, high mechanical stability is reported.

Recent Developments in Antimicrobial Polymers: A Review

PubMed Central

Santos, Madson R. E.; Fonseca, Ana C.; Mendonça, Patrícia V.; Branco, Rita; Serra, Arménio C.; Morais, Paula V.; Coelho, Jorge F. J.

2016-01-01

Antimicrobial polymers represent a very promising class of therapeutics with unique characteristics for fighting microbial infections. As the classic antibiotics exhibit an increasingly low capacity to effectively act on microorganisms, new solutions must be developed. The importance of this class of materials emerged from the uncontrolled use of antibiotics, which led to the advent of multidrug-resistant microbes, being nowadays one of the most serious public health problems. This review presents a critical discussion of the latest developments involving the use of different classes of antimicrobial polymers. The synthesis pathways used to afford macromolecules with antimicrobial properties, as well as the relationship between the structure and performance of these materials are discussed. PMID:28773721

Bacopa monniera leaf extract ameliorates hypobaric hypoxia induced spatial memory impairment.

PubMed

Hota, Sunil Kumar; Barhwal, Kalpana; Baitharu, Iswar; Prasad, Dipti; Singh, Shashi Bala; Ilavazhagan, Govindasamy

2009-04-01

Hypobaric hypoxia induced memory impairment has been attributed to several factors including increased oxidative stress, depleted mitochondrial bioenergetics, altered neurotransmission and apoptosis. This multifactorial response of the brain to hypobaric hypoxia limits the use of therapeutic agents that target individual pathways for ameliorating hypobaric hypoxia induced memory impairment. The present study aimed at exploring the therapeutic potential of a bacoside rich leaf extract of Bacopa monniera in improving the memory functions in hypobaric conditions. The learning ability was evaluated in male Sprague Dawley rats along with memory retrieval following exposure to hypobaric conditions simulating an altitude of 25,000 ft for different durations. The effect of bacoside administration on apoptosis, cytochrome c oxidase activity, ATP levels, and oxidative stress markers and on plasma corticosterone levels was investigated. Expression of NR1 subunit of N-methyl-d-aspartate receptors, neuronal cell adhesion molecules and was also studied along with CREB phosphorylation to elucidate the molecular mechanisms of bacoside action. Bacoside administration was seen to enhance learning ability in rats along with augmentation in memory retrieval and prevention of dendritic atrophy following hypoxic exposure. In addition, it decreased oxidative stress, plasma corticosterone levels and neuronal degeneration. Bacoside administration also increased cytochrome c oxidase activity along with a concomitant increase in ATP levels. Hence, administration of bacosides could be a useful therapeutic strategy in ameliorating hypobaric hypoxia induced cognitive dysfunctions and other related neurological disorders.

The past, the future and the biology of memory storage.

PubMed Central

Kandel, E R; Pittenger, C

1999-01-01

We here briefly review a century of accomplishments in studying memory storage and delineate the two major questions that have dominated thinking in this area: the systems question of memory, which concerns where in the brain storage occurs; and the molecular question of memory, which concerns the mechanisms whereby memories are stored and maintained. We go on to consider the themes that memory research may be able to address in the 21st century. Finally, we reflect on the clinical and societal import of our increasing understanding of the mechanisms of memory, discussing possible therapeutic approaches to diseases that manifest with disruptions of learning and possible ethical implication of the ability, which is on the horizon, to ameliorate or even enhance human memory. PMID:10670023

Antibody Therapeutics in Oncology.

PubMed

Wold, Erik D; Smider, Vaughn V; Felding, Brunhilde H

2016-03-01

One of the newer classes of targeted cancer therapeutics is monoclonal antibodies. Monoclonal antibody therapeutics are a successful and rapidly expanding drug class due to their high specificity, activity, favourable pharmacokinetics, and standardized manufacturing processes. Antibodies are capable of recruiting the immune system to attack cancer cells through complement-dependent cytotoxicity or antibody dependent cellular cytotoxicity. In an ideal scenario the initial tumor cell destruction induced by administration of a therapeutic antibody can result in uptake of tumor associated antigens by antigen-presenting cells, establishing a prolonged memory effect. Mechanisms of direct tumor cell killing by antibodies include antibody recognition of cell surface bound enzymes to neutralize enzyme activity and signaling, or induction of receptor agonist or antagonist activity. Both approaches result in cellular apoptosis. In another and very direct approach, antibodies are used to deliver drugs to target cells and cause cell death. Such antibody drug conjugates (ADCs) direct cytotoxic compounds to tumor cells, after selective binding to cell surface antigens, internalization, and intracellular drug release. Efficacy and safety of ADCs for cancer therapy has recently been greatly advanced based on innovative approaches for site-specific drug conjugation to the antibody structure. This technology enabled rational optimization of function and pharmacokinetics of the resulting conjugates, and is now beginning to yield therapeutics with defined, uniform molecular characteristics, and unprecedented promise to advance cancer treatment.

Serotonin, neural markers, and memory

PubMed Central

Meneses, Alfredo

2015-01-01

Diverse neuropsychiatric disorders present dysfunctional memory and no effective treatment exits for them; likely as result of the absence of neural markers associated to memory. Neurotransmitter systems and signaling pathways have been implicated in memory and dysfunctional memory; however, their role is poorly understood. Hence, neural markers and cerebral functions and dysfunctions are revised. To our knowledge no previous systematic works have been published addressing these issues. The interactions among behavioral tasks, control groups and molecular changes and/or pharmacological effects are mentioned. Neurotransmitter receptors and signaling pathways, during normal and abnormally functioning memory with an emphasis on the behavioral aspects of memory are revised. With focus on serotonin, since as it is a well characterized neurotransmitter, with multiple pharmacological tools, and well characterized downstream signaling in mammals' species. 5-HT1A, 5-HT4, 5-HT5, 5-HT6, and 5-HT7 receptors as well as SERT (serotonin transporter) seem to be useful neural markers and/or therapeutic targets. Certainly, if the mentioned evidence is replicated, then the translatability from preclinical and clinical studies to neural changes might be confirmed. Hypothesis and theories might provide appropriate limits and perspectives of evidence. PMID:26257650

Biomedical applications of thermally activated shape memory polymers†

PubMed Central

Small, Ward; Singhal, Pooja; Wilson, Thomas S.

2011-01-01

Shape memory polymers (SMPs) are smart materials that can remember a primary shape and can return to this primary shape from a deformed secondary shape when given an appropriate stimulus. This property allows them to be delivered in a compact form via minimally invasive surgeries in humans, and deployed to achieve complex final shapes. Here we review the various biomedical applications of SMPs and the challenges they face with respect to actuation and biocompatibility. While shape memory behavior has been demonstrated with heat, light and chemical environment, here we focus our discussion on thermally stimulated SMPs. PMID:21258605

Magnetically Controllable Polymer Nanotubes from a Cyclized Crosslinker for Site-Specific Delivery of Doxorubicin

PubMed Central

Newland, Ben; Leupelt, Daniel; Zheng, Yu; Thomas, Laurent S. V.; Werner, Carsten; Steinhart, Martin; Wang, Wenxin

2015-01-01

Externally controlled site specific drug delivery could potentially provide a means of reducing drug related side effects whilst maintaining, or perhaps increasing therapeutic efficiency. The aim of this work was to develop a nanoscale drug carrier, which could be loaded with an anti-cancer drug and be directed by an external magnetic field. Using a single, commercially available monomer and a simple one-pot reaction process, a polymer was synthesized and crosslinked within the pores of an anodized aluminum oxide template. These polymer nanotubes (PNT) could be functionalized with iron oxide nanoparticles for magnetic manipulation, without affecting the large internal pore, or inherent low toxicity. Using an external magnetic field the nanotubes could be regionally concentrated, leaving areas devoid of nanotubes. Lastly, doxorubicin could be loaded to the PNTs, causing increased toxicity towards neuroblastoma cells, rendering a platform technology now ready for adaptation with different nanoparticles, degradable pre-polymers, and various therapeutics. PMID:26619814

Magnetically Controllable Polymer Nanotubes from a Cyclized Crosslinker for Site-Specific Delivery of Doxorubicin

NASA Astrophysics Data System (ADS)

Newland, Ben; Leupelt, Daniel; Zheng, Yu; Thomas, Laurent S. V.; Werner, Carsten; Steinhart, Martin; Wang, Wenxin

2015-12-01

Externally controlled site specific drug delivery could potentially provide a means of reducing drug related side effects whilst maintaining, or perhaps increasing therapeutic efficiency. The aim of this work was to develop a nanoscale drug carrier, which could be loaded with an anti-cancer drug and be directed by an external magnetic field. Using a single, commercially available monomer and a simple one-pot reaction process, a polymer was synthesized and crosslinked within the pores of an anodized aluminum oxide template. These polymer nanotubes (PNT) could be functionalized with iron oxide nanoparticles for magnetic manipulation, without affecting the large internal pore, or inherent low toxicity. Using an external magnetic field the nanotubes could be regionally concentrated, leaving areas devoid of nanotubes. Lastly, doxorubicin could be loaded to the PNTs, causing increased toxicity towards neuroblastoma cells, rendering a platform technology now ready for adaptation with different nanoparticles, degradable pre-polymers, and various therapeutics.

[Eye contact effects: A therapeutic issue?

PubMed

Baltazar, M; Conty, L

2016-12-01

The perception of a direct gaze - that is, of another individual's gaze directed at the observer that leads to eye contact - is known to influence a wide range of cognitive processes and behaviors. We stress that these effects mainly reflect positive impacts on human cognition and may thus be used as relevant tools for therapeutic purposes. In this review, we aim (1) to provide an exhaustive review of eye contact effects while discussing the limits of the dominant models used to explain these effects, (2) to illustrate the therapeutic potential of eye contact by targeting those pathologies that show both preserved gaze processing and deficits in one or several functions that are targeted by the eye contact effects, and (3) to propose concrete ways in which eye contact could be employed as a therapeutic tool. (1) We regroup the variety of eye contact effects into four categories, including memory effects, activation of prosocial behavior, positive appraisals of self and others and the enhancement of self-awareness. We emphasize that the models proposed to account for these effects have a poor predictive value and that further descriptions of these effects is needed. (2) We then emphasize that people with pathologies that affect memory, social behavior, and self and/or other appraisal, and self-awareness could benefit from eye contact effects. We focus on depression, autism and Alzheimer's disease to illustrate our proposal. To our knowledge, no anomaly of eye contact has been reported in depression. Patients suffering from Alzheimer disease, at the early and moderate stage, have been shown to maintain a normal amount of eye contact with their interlocutor. We take into account that autism is controversial regarding whether gaze processing is preserved or altered. In the first view, individuals are thought to elude or omit gazing at another's eyes while in the second, individuals are considered to not be able to process the gaze of others. We adopt the first stance

The effects of heterogeneities on memory-dependent diffusion

NASA Astrophysics Data System (ADS)

Adib, Farhad; Neogi, P.

1993-07-01

Case II diffusion is often seen in glassy polymers, where the mass uptake in sorption is proportional to time t instead of sqrt{t}. A memory dependent diffusion is needed to explain such effects, where the relaxation function used to describe the memory effect has a characteristic time. The ratio of this time to the overall diffusion times is the diffusional Deborah number. Simple models show that case II results when the Deborah number is around one, that is, when the two time scales are comparable. Under investigation are the possible effects of the fact that the glassy polymers are heterogeneous over molecular scales. The averaging form given by DiMarzio and Sanchez has been used to obtain the averaged response. The calculated dynamics of sorption show that whereas case II is still observed, the long term tails change dramatically from the oscillatory to torpid, to chaotic, which are all observed in the experiments. The Deborah number defined here in a self-consistent manner collapses in those cases, but causes no other ill-effects.

Polymer-drug conjugates: origins, progress to date and future directions.

PubMed

Kopeček, Jindřich

2013-01-01

This overview focuses on bioconjugates of water-soluble polymers with low molecular weight drugs and proteins. After a short discussion of the origins of the field, the state-of-the-art is reviewed. Then research directions needed for the acceleration of the translation of nanomedicines into the clinic are outlined. Two most important directions, synthesis of backbone degradable polymer carriers and drug-free macromolecular therapeutics, a new paradigm in drug delivery, are discussed in detail. Finally, the future perspectives of the field are briefly discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

Polymer Architecture Effects in Confined Geometry: Molecular Dynamics Simulation Study

NASA Astrophysics Data System (ADS)

Wijesinghe, Sidath; Perahia, Dvora; Grest, Gary

Luminescent rigid polymers confined into nanoparticles, or polydots, are emerging as a promising tool for nano medicine. The constrained architecture of a rigid backbone trapped in nano-dimensions results in photophysics that differs from that of spontaneously assembled rigid polymers. Incorporating ionizable functionalities in the polymers, often required for therapeutics, impacts the polymer conformation in solution. Here we report fully atomistic molecular dynamics simulations on the structure of dialkyl p-phenylene ethynylene confined into polydots. We find that the structure and thermal stability of polydots are sensitive to both the molecular weight n and the carboxylation fraction f. At room temperature , polydots remain confined regardless of n and f . However, as temperature is increased, polydots with lower n or f rearrange whereas polydots with higher n or fremain confined, though no direct clustering of the ionic groups was observed. NSF CHE 1308298 is acknowledged.

HER2 Targeted Breast Cancer Therapy with Switchable "Off/On" Multifunctional "Smart" Magnetic Polymer Core-Shell Nanocomposites.

PubMed

Vivek, Raju; Thangam, Ramar; Kumar, Selvaraj Rajesh; Rejeeth, Chandrababu; Kumar, Gopal Senthil; Sivasubramanian, Srinivasan; Vincent, Savariar; Gopi, Dhanaraj; Kannan, Soundarapandian

2016-01-27

Multifunctional magnetic polymer nanocombinations are gaining importance in cancer nanotheranostics due to their safety and their potential in delivering targeted functions. Herein, we report a novel multifunctional core-shell magnetic polymer therapeutic nanocomposites (NCs) exhibiting pH dependent "Off-On" release of drug against breast cancer cells. The NCs are intact in blood circulation ("Off" state), i.e., at physiological pH, whereas activated ("On" state) at intracellular acidic pH environment of the targeted breast cancer cells. The NCs are prepared by coating the cannonball (iron nanocore) with hydrophobic nanopockets of pH-responsive poly(d,l-lactic-co-glycolic acid) (PLGA) polymer nanoshell that allows efficient loading of therapeutics. Further, the nanocore-polymer shell is stabilized by poly(vinylpyrrolidone) (PVP) and functionalized with a targeting HER2 ligand. The prepared Her-Fe3O4@PLGA-PVP nanocomposites facilitate packing of anticancer drug (Tamoxifen) without premature release in the bloodstream, recognizing the target cells through binding of Herceptin antibody to HER2, a cell surface receptor expressed by breast cancer cells to promote HER2 receptor mediated endocytosis and finally releasing the drug at the intracellular site of tumor cells ("On" state) to induce apoptosis. The therapeutic efficiency of hemo/cytocompatible NCs drug delivery system (DDS) in terms of targeted delivery and sustained release of therapeutic agent against breast cancer cells was substantiated by in vitro and in vivo studies. The multifunctional properties of Her-Tam-Fe3O4@PLGA-PVP NCs may open up new avenues in cancer therapy through overcoming the limitations of conventional cancer therapy.

Characterizing filamentary switching in resistive memories (Presentation Recording)

NASA Astrophysics Data System (ADS)

Busby, Yan; Pireaux, Jean-Jacques

2015-09-01

Characterizing filamentary switching in resistive memories For many organic, inorganic and hybrid memory devices the resistive switching mechanism is well known to rely on filament formation [1]. This implies that localized conductive paths are established between the two terminal electrodes during the forming step. This filaments sustain the current flow when the memory is in the low conductive state and they can be ruptured and possibly re-formed for more than hundreds of I-V cycles. The nature and morphology of filaments has been long time debated especially for organic memories. The filament size, density and formation mechanism have been very challenging to be characterized, and need appropriate experimental techniques. However, filaments in organic memories have been recently identified and characterized by cross-section transmission electron microscopy (TEM), conductive-AFM, AFM-tomography and through depth profile analysis combining Time-of-flight secondary ions mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS). In particular, 3D spectroscopic images obtained with ToF-SIMS give access for the first time to filament formation process and rupture mechanism. From these results, a clear picture of the filament(s) dynamics during memory operation can be drawn. In this contribution, recent results showing filaments in memories based on different structures and architectures will be discussed. The memories are based on insulating polymers (polystyrene [2] and poly methyl methacrylate [3]), conductive polymers/nanocomposites (polyera N1400 with metal NPs [4]), and small semiconducting molecules (Tris(8-hydroxyquinolinato)aluminium - Alq3 [5]). The results show that resistive switching clearly involves the inhomogeneous metal diffusion in the organic layer taking place during the top electrode deposition and during memory operation. This may be of great relevance in many other organic electronics applications. REFERENCES [1] S. Nau, S. Sax, E

Examining Object Location and Object Recognition Memory in Mice

PubMed Central

Vogel-Ciernia, Annie; Wood, Marcelo A.

2014-01-01

Unit Introduction The ability to store and recall our life experiences defines a person's identity. Consequently, the loss of long-term memory is a particularly devastating part of a variety of cognitive disorders, diseases and injuries. There is a great need to develop therapeutics to treat memory disorders, and thus a variety of animal models and memory paradigms have been developed. Mouse models have been widely used both to study basic disease mechanisms and to evaluate potential drug targets for therapeutic development. The relative ease of genetic manipulation of Mus musculus has led to a wide variety of genetically altered mice that model cognitive disorders ranging from Alzheimer's disease to autism. Rodents, including mice, are particularly adept at encoding and remembering spatial relationships, and these long-term spatial memories are dependent on the medial temporal lobe of the brain. These brain regions are also some of the first and most heavily impacted in disorders of human memory including Alzheimer's disease. Consequently, some of the simplest and most commonly used tests of long-term memory in mice are those that examine memory for objects and spatial relationships. However, many of these tasks, such as Morris water maze and contextual fear conditioning, are dependent upon the encoding and retrieval of emotionally aversive and inherently stressful training events. While these types of memories are important, they do not reflect the typical day-to-day experiences or memories most commonly affected in human disease. In addition, stress hormone release alone can modulate memory and thus obscure or artificially enhance these types of tasks. To avoid these sorts of confounds, we and many others have utilized tasks testing animals’ memory for object location and novel object recognition. These tasks involve exploiting rodents’ innate preference for novelty, and are inherently not stressful. In this protocol we detail how memory for object location

Ocular pharmacokinetic study using T₁ mapping and Gd-chelate- labeled polymers.

PubMed

Shi, Xianfeng; Liu, Xin; Wu, Xueming; Lu, Zheng-Rong; Li, S Kevin; Jeong, Eun-Kee

2011-12-01

Recent advances in drug discovery have led to the development of a number of therapeutic macromolecules for treatment of posterior eye diseases. We aimed to investigate the clearance of macromolecular contrast probes (polymers conjugated with Gd-chelate) in the vitreous after intravitreal injections with the recently developed ms-DSEPI-T12 MRI and to examine the degradation of disulfide-containing biodegradable polymers in the vitreous humor in vivo. Intravitreal injections of model contrast agents poly[N-(2-hydroxypropyl)methacrylamide]-GG-1,6-hexanediamine-(Gd-DO3A), biodegradable (Gd-DTPA)-cystine copolymers, and MultiHance were performed in rabbits; their distribution and elimination from the vitreous after injections were determined by MRI. Times for macromolecular contrast agents to decrease to half their initial concentrations in the vitreous ranged from 0.4-1.3 days post-injection. Non-biodegradable polymers demonstrated slower vitreal clearance than those of disulfide-biodegradable polymers. Biodegradable polymers had similar clearance as MultiHance. Usefulness of T(1) mapping and ms-DSEPI-T12 MRI to study ocular pharmacokinetics was demonstrated. Results suggest an enzymatic degradation mechanism for the disulfide linkage in polymers in the vitreous leading to breakup of polymers in vitreous humor over time.

Polymer-encapsulated organic nanoparticles for fluorescence and photoacoustic imaging.

PubMed

Li, Kai; Liu, Bin

2014-09-21

Polymer encapsulated organic nanoparticles have recently attracted increasing attention in the biomedical field because of their unique optical properties, easy fabrication and outstanding performance as imaging and therapeutic agents. Of particular importance is the polymer encapsulated nanoparticles containing conjugated polymers (CP) or fluorogens with aggregation induced emission (AIE) characteristics as the core, which have shown significant advantages in terms of tunable brightness, superb photo- and physical stability, good biocompatibility, potential biodegradability and facile surface functionalization. In this review, we summarize the latest advances in the development of polymer encapsulated CP and AIE fluorogen nanoparticles, including preparation methods, material design and matrix selection, nanoparticle fabrication and surface functionalization for fluorescence and photoacoustic imaging. We also discuss their specific applications in cell labeling, targeted in vitro and in vivo imaging, blood vessel imaging, cell tracing, inflammation monitoring and molecular imaging. We specially focus on strategies to fine-tune the nanoparticle property (e.g. size and fluorescence quantum yield) through precise engineering of the organic cores and careful selection of polymer matrices. The review also highlights the merits and limitations of these nanoparticles as well as strategies used to overcome the limitations. The challenges and perspectives for the future development of polymer encapsulated organic nanoparticles are also discussed.

Polymer – drug conjugates: Origins, progress to date and future directions

PubMed Central

Kopeček, Jindřich

2012-01-01

This overview focuses on bioconjugates of water-soluble polymers with low molecular weight drugs and proteins. After a short discussion of the origins of the field, the state-of-the-art is reviewed. Then research directions needed for the acceleration of the translation of nanomedicines into the clinic are outlined. Two most important directions, synthesis of backbone degradable polymer carriers and drug-free macromolecular therapeutics, a new paradigm in drug delivery, are discussed in detail. Finally, the future perspectives of the field are briefly discussed. PMID:23123294

Engineering of blended nanoparticle platform for delivery of mitochondria-acting therapeutics

PubMed Central

Marrache, Sean; Dhar, Shanta

2012-01-01

Mitochondrial dysfunctions cause numerous human disorders. A platform technology based on biodegradable polymers for carrying bioactive molecules to the mitochondrial matrix could be of enormous potential benefit in treating mitochondrial diseases. Here we report a rationally designed mitochondria-targeted polymeric nanoparticle (NP) system and its optimization for efficient delivery of various mitochondria-acting therapeutics by blending a targeted poly(d,l-lactic-co-glycolic acid)-block (PLGA-b)-poly(ethylene glycol) (PEG)-triphenylphosphonium (TPP) polymer (PLGA-b-PEG-TPP) with either nontargeted PLGA-b-PEG-OH or PLGA-COOH. An optimized formulation was identified through in vitro screening of a library of charge- and size-varied NPs, and mitochondrial uptake was studied by qualitative and quantitative investigations of cytosolic and mitochondrial fractions of cells treated with blended NPs composed of PLGA-b-PEG-TPP and a triblock copolymer containing a fluorescent quantum dot, PLGA-b-PEG-QD. The versatility of this platform was demonstrated by studying various mitochondria-acting therapeutics for different applications, including the mitochondria-targeting chemotherapeutics lonidamine and α-tocopheryl succinate for cancer, the mitochondrial antioxidant curcumin for Alzheimer’s disease, and the mitochondrial uncoupler 2,4-dinitrophenol for obesity. These biomolecules were loaded into blended NPs with high loading efficiencies. Considering efficacy, the targeted PLGA-b-PEG-TPP NP provides a remarkable improvement in the drug therapeutic index for cancer, Alzheimer’s disease, and obesity compared with the nontargeted construct or the therapeutics in their free form. This work represents the potential of a single, programmable NP platform for the diagnosis and targeted delivery of therapeutics for mitochondrial dysfunction-related diseases. PMID:22991470

Glomerular disease augments kidney accumulation of synthetic anionic polymers.

PubMed

Liu, Gary W; Prossnitz, Alexander N; Eng, Diana G; Cheng, Yilong; Subrahmanyam, Nithya; Pippin, Jeffrey W; Lamm, Robert J; Ngambenjawong, Chayanon; Ghandehari, Hamidreza; Shankland, Stuart J; Pun, Suzie H

2018-06-02

Polymeric drug carriers can alter the pharmacokinetics of their drug cargoes, thereby improving drug therapeutic index and reducing side effects. Understanding and controlling polymer properties that drive tissue-specific accumulation is critical in engineering targeted drug delivery systems. For kidney disease applications, targeted drug delivery to renal cells that reside beyond the charge- and size-selective glomerular filtration barrier could have clinical potential. However, there are limited reports on polymer properties that might enhance kidney accumulation. Here, we studied the effects of molecular weight and charge on the in vivo kidney accumulation of polymers in health and disease. We synthesized a panel of well-defined polymers by atom transfer radical polymerization to answer several questions. First, the biodistribution of low molecular weight (23-27 kDa) polymers composed of various ratios of neutral:anionic monomers (1:0, 1:1, 1:4) in normal mice was determined. Then, highly anionic (1:4 monomer ratio) low molecular and high molecular weight (47 kDa) polymers were tested in both normal and experimental focal segmental glomerulosclerosis (FSGS) mice, a model that results in loss of glomerular filtration selectivity. Through these studies, we observed that kidney-specific polymer accumulation increases with anionic monomer content, but not molecular weight; experimental FSGS increases kidney accumulation of anionic polymers; and anionic polymers accumulate predominantly in proximal tubule cells, with some distribution in kidney glomeruli. These findings can be applied to the design of polymeric drug carriers to enhance or mitigate kidney accumulation. Copyright © 2018 Elsevier Ltd. All rights reserved.

Self-healing polymers and composites based on thermal activation

NASA Astrophysics Data System (ADS)

Wang, Ying; Bolanos, Ed; Wudl, Fred; Hahn, Thomas; Kwok, Nathan

2007-04-01

Structural polymer composites are susceptible to premature failure in the form of microcracks in the matrix. Although benign initially when they form, these matrix cracks tend to coalesce and lead in service to critical damage modes such as ply delamination. The matrix cracks are difficult to detect and almost impossible to repair because they form inside the composite laminate. Therefore, polymers with self-healing capability would provide a promising potential to minimize maintenance costs while extending the service lifetime of composite structures. In this paper we report on a group of polymers and their composites which exhibit mendable property upon heating. The failure and healing mechanisms of the polymers involve Diels-Alder (DA) and retro-Diels-Alder (RDA) reactions on the polymer back-bone chain, which are thermally reversible reactions requiring no catalyst. The polymers exhibited good healing property in bulk form. Composite panels were prepared by sandwiching the monomers between carbon fiber fabric layers and cured in autoclave. Microcracks were induced on the resin-rich surface of composite with Instron machine at room temperature by holding at 1% strain for 1 min. The healing ability of the composite was also demonstrated by the disappearance of microcracks after heating. In addition to the self-healing ability, the polymers and composites also exhibited shape memory property. These unique properties may provide the material multi-functional applications. Resistance heating of traditional composites and its applicability in self-healing composites is also studied to lay groundwork for a fully integrated self-healing composite.

Multiblock thermoplastic polyurethanes for biomedical and shape memory applications

NASA Astrophysics Data System (ADS)

Gu, Xinzhu

Polyurethanes are a class of polymers that are capable of tailoring the overall polymer structure and thus final properties by many factors. The great potential in tailoring polymer structures imparts PUs unique mechanical properties and good cytocompatibility, which make them good candidates for many biomedical devices. In this dissertation, three families of multiblock thermoplastic polyurethanes are synthesized and characterized for biomedical and shape memory applications. In the first case described in Chapters 2, 3 and 4, a novel family of multiblock thermoplastic polyurethanes consisting of poly(ɛ-caprolactone) (PCL) and poly(ethylene glycol) (PEG) are presented. These materials were discovered to be very durable, with strain-to-break higher than 1200%. Heat-triggered reversible plasticity shape memory (RPSM) was observed, where the highly deformed samples completely recovered their as-cast shape within one minute when heating above the transition temperature. Instead of conventional "hard" blocks, entanglements, which result from high molecular weight, served as the physical crosslinks in this system, engendering shape recovery and preventing flow. Moreover, water-triggered shape memory effect of PCL-PEG TPUs is explored, wherein water permeated into the initially oriented PEG domains, causing rapid shape recovery toward the equilibrium shape upon contact with liquid water. The recovery behavior is found to be dependent on PEG weight percentage in the copolymers. By changing the material from bulk film to electrospun fibrous mat, recovery speed was greatly accelerated. The rate of water recovery was manipulated through structural variables, including thickness of bulk film and diameter of e-spun webs. A new, yet simple shape memory cycle, "wet-fixing" is also reported, where both the fixing and recovery ratios can be greatly improved. A detailed microstructural study on one particular composition is presented, revealing the evolution of microphase

Thermomechanical behavior of a two-way shape memory composite actuator

NASA Astrophysics Data System (ADS)

Ge, Qi; Westbrook, Kristofer K.; Mather, Patrick T.; Dunn, Martin L.; Qi, H. Jerry

2013-05-01

Shape memory polymers (SMPs) are a class of smart materials that can fix a temporary shape and recover to their permanent (original) shape in response to an environmental stimulus such as heat, electricity, or irradiation, among others. Most SMPs developed in the past can only demonstrate the so-called one-way shape memory effect; i.e., one programming step can only yield one shape memory cycle. Recently, one of the authors (Mather) developed a SMP that exhibits both one-way shape memory (1W-SM) and two-way shape memory (2W-SM) effects (with the assistance of an external load). This SMP was further used to develop a free-standing composite actuator with a nonlinear reversible actuation under thermal cycling. In this paper, a theoretical model for the PCO SMP based composite actuator was developed to investigate its thermomechanical behavior and the mechanisms for the observed phenomena during the actuation cycles, and to provide insight into how to improve the design.

Stabilization of Proteins by Polymer Conjugation via ATRP

DTIC Science & Technology

2008-08-31

to increase their solubility and utility in organic solvents and to increase their stability in body. Protein-initiated ATRP would enable us to... Solvent solubilization, therapeutic proteins, hydrophilic polymers, protein stabilization Lance Mabus, Jason Berberich, Bhalchandra Lele, Virginia Depp... solvents and to increase their stability in body. Protein-initiated ATRP would enable us to overcome many problems in conventional technology that

Increasing dimension of structures by 4D printing shape memory polymers via fused deposition modeling

NASA Astrophysics Data System (ADS)

Hu, G. F.; Damanpack, A. R.; Bodaghi, M.; Liao, W. H.

2017-12-01

The main objective of this paper is to introduce a 4D printing method to program shape memory polymers (SMPs) during fabrication process. Fused deposition modeling (FDM) as a filament-based printing method is employed to program SMPs during depositing the material. This method is implemented to fabricate complicated polymeric structures by self-bending features without need of any post-programming. Experiments are conducted to demonstrate feasibility of one-dimensional (1D)-to 2D and 2D-to-3D self-bending. It is shown that 3D printed plate structures can transform into masonry-inspired 3D curved shell structures by simply heating. Good reliability of SMP programming during printing process is also demonstrated. A 3D macroscopic constitutive model is established to simulate thermo-mechanical features of the printed SMPs. Governing equations are also derived to simulate programming mechanism during printing process and shape change of self-bending structures. In this respect, a finite element formulation is developed considering von-Kármán geometric nonlinearity and solved by implementing iterative Newton-Raphson scheme. The accuracy of the computational approach is checked with experimental results. It is demonstrated that the theoretical model is able to replicate the main characteristics observed in the experiments. This research is likely to advance the state of the art FDM 4D printing, and provide pertinent results and computational tool that are instrumental in design of smart materials and structures with self-bending features.

Polymeric nanoparticulate system augmented the anticancer therapeutic efficacy of gemcitabine.

PubMed

Arias, José L; Reddy, L Harivardhan; Couvreur, Patrick

2009-09-01

Gemcitabine hydrochloride is an anticancer nucleoside analogue indicated in clinic for the treatment of various solid tumors. Although this drug has been demonstrated to display anticancer activity against a wide variety of tumors, it is needed to be administered at high doses to elicit the required therapeutic response, simultaneously leading to severe adverse effects. We hypothesized that the efficient delivery of gemcitabine to tumors using a biodegradable carrier system could reduce the dose required to elicit sufficient therapeutic response. Thus, we have developed a nanoparticle formulation of gemcitabine suitable for parenteral administration based on the biodegradable polymer poly(octylcyanoacrylate) (POCA). The nanoparticles were synthesized by anionic polymerization of the corresponding monomer. Two drug loading methods were analyzed: the first one based on gemcitabine surface adsorption onto the preformed nanoparticles, and the second method being gemcitabine addition before the polymerization process leading to drug entrapment in the polymeric network. A detailed investigation of the capabilities of the polymer particles to load this drug is described. Gemcitabine entrapment into the polymer matrix yielded a higher drug loading and a slower drug release profile as compared with drug adsorption procedure. The main factors determining the gemcitabine incorporation to the polymer network were the nanoparticles preparation procedure, the monomer concentration, the surfactant concentration, the pH, and the drug concentration. The release kinetic of gemcitabine was found to be controlled by the pH and the type of drug incorporation. The cytotoxicity studies performed on L1210 tumor cells revealed a similar anticancer activity of the gemcitabine-loaded POCA (GPOCA) nanoparticle as free gemcitabine. Following intravenous administration into the mice bearing L1210 wt subcutaneous tumor, the GPOCA nanoparticles displayed significantly greater anticancer activity

Delivery of local therapeutics to the brain: working toward advancing treatment for malignant gliomas.

PubMed

Chaichana, Kaisorn L; Pinheiro, Leon; Brem, Henry

2015-03-01

Malignant gliomas, including glioblastoma and anaplastic astrocytomas, are characterized by their propensity to invade surrounding brain parenchyma, making curative resection difficult. These tumors typically recur within two centimeters of the resection cavity even after gross total removal. As a result, there has been an emphasis on developing therapeutics aimed at achieving local disease control. In this review, we will summarize the current developments in the delivery of local therapeutics, namely direct injection, convection-enhanced delivery and implantation of drug-loaded polymers, as well as the application of these therapeutics in future methods including microchip drug delivery and local gene therapy.

Delivery of local therapeutics to the brain: working toward advancing treatment for malignant gliomas

PubMed Central

Chaichana, Kaisorn L; Pinheiro, Leon; Brem, Henry

2015-01-01

Malignant gliomas, including glioblastoma and anaplastic astrocytomas, are characterized by their propensity to invade surrounding brain parenchyma, making curative resection difficult. These tumors typically recur within two centimeters of the resection cavity even after gross total removal. As a result, there has been an emphasis on developing therapeutics aimed at achieving local disease control. In this review, we will summarize the current developments in the delivery of local therapeutics, namely direct injection, convection-enhanced delivery and implantation of drug-loaded polymers, as well as the application of these therapeutics in future methods including microchip drug delivery and local gene therapy. PMID:25853310

Self-assembling nucleic acid delivery vehicles via linear, water-soluble, cyclodextrin-containing polymers.

PubMed

Davis, M E; Pun, S H; Bellocq, N C; Reineke, T M; Popielarski, S R; Mishra, S; Heidel, J D

2004-01-01

Non-viral (synthetic) nucleic acid delivery systems have the potential to provide for the practical application of nucleic acid-based therapeutics. We have designed and prepared a tunable, non-viral nucleic acid delivery system that self-assembles with nucleic acids and centers around a new class of polymeric materials; namely, linear, water-soluble cyclodextrin-containing polymers. The relationships between polymer structure and gene delivery are illustrated, and the roles of the cyclodextrin moieties for minimizing toxicity and forming inclusion complexes in the self-assembly processes are highlighted. This vehicle is the first example of a polymer-based gene delivery system formed entirely by self-assembly.

Regulating Critical Period Plasticity: Insight from the Visual System to Fear Circuitry for Therapeutic Interventions

PubMed Central

Nabel, Elisa M.; Morishita, Hirofumi

2013-01-01

Early temporary windows of heightened brain plasticity called critical periods developmentally sculpt neural circuits and contribute to adult behavior. Regulatory mechanisms of visual cortex development – the preeminent model of experience-dependent critical period plasticity-actively limit adult plasticity and have proved fruitful therapeutic targets to reopen plasticity and rewire faulty visual system connections later in life. Interestingly, these molecular mechanisms have been implicated in the regulation of plasticity in other functions beyond vision. Applying mechanistic understandings of critical period plasticity in the visual cortex to fear circuitry may provide a conceptual framework for developing novel therapeutic tools to mitigate aberrant fear responses in post traumatic stress disorder. In this review, we turn to the model of experience-dependent visual plasticity to provide novel insights for the mechanisms regulating plasticity in the fear system. Fear circuitry, particularly fear memory erasure, also undergoes age-related changes in experience-dependent plasticity. We consider the contributions of molecular brakes that halt visual critical period plasticity to circuitry underlying fear memory erasure. A major molecular brake in the visual cortex, perineuronal net formation, recently has been identified in the development of fear systems that are resilient to fear memory erasure. The roles of other molecular brakes, myelin-related Nogo receptor signaling and Lynx family proteins – endogenous inhibitors for nicotinic acetylcholine receptor, are explored in the context of fear memory plasticity. Such fear plasticity regulators, including epigenetic effects, provide promising targets for therapeutic interventions. PMID:24273519

Clinical Holistic Medicine: How to Recover Memory Without “Implanting” Memories in Your Patient

PubMed Central

Ventegodt, Søren; Kandel, Isack; Merrick, Joav

2007-01-01

Every therapeutic strategy and system teach us the philosophy of the treatment system to the patient, but often this teaching is subliminal and the philosophical impact must be seen as “implanted philosophy”, which gives distorted interpretations of past events called “implanted memories”. Based on the understanding of the connection between “implanted memory” and “implanted philosophy” we have developed a strategy for avoiding implanting memories arising from one of the seven most common causes of implanted memories in psychodynamic therapy: 1) Satisfying own expectancies, 2) pleasing the therapist, 3) transferences and counter transferences, 4) as source of mental and emotional order, 5) as emotional defence, 6) as symbol and 7) from implanted philosophy. Freud taught us that child sexuality is “polymorphously perverted”, meaning that all kinds of sexuality is present at least potentially with the little child; and in dreams consciousness often go back to the earlier stages of development, potentially causing all kinds of sexual dreams and fantasies, which can come up in therapy and look like real memories. The therapist working with psychodynamic psychotherapy, clinical holistic medicine, psychiatry, and emotionally oriented bodywork, should be aware of the danger of implanting philosophy and memories. Implanted memories and implanted philosophy must be carefully handled and de-learned before ending the therapy. In conclusion “clinical holistic medicine” has developed a strategy for avoiding implanting memories. PMID:17891319

Cyclic peptides as potential therapeutic agents for skin disorders.

PubMed

Namjoshi, Sarika; Benson, Heather A E

2010-01-01

There is an increasing understanding of the role of peptides in normal skin function and skin disease. With this knowledge, there is significant interest in the application of peptides as therapeutics in skin disease or as cosmeceuticals to enhance skin appearance. In particular, antimicrobial peptides and those involved in inflammatory processes provide options for the development of new therapeutic directions in chronic skin conditions such as psoriasis and dermatitis. To exploit their potential, it is essential that these peptides are delivered to their site of action in active form and in sufficient quantity to provide the desired effect. Many polymers permeate the skin poorly and are vulnerable to enzymatic degradation. Synthesis of cyclic peptide derivatives can substantially alter the physicochemical characteristics of the peptide with the potential to improve its skin permeation. In addition, cyclization can stabilize the peptide structure and thereby increase its stability. This review describes the role of cyclic peptides in the skin, examples of current cyclic peptide therapeutic products, and the potential for cyclic peptides as dermatological therapeutics and cosmeceuticals.

Real-time Monitoring of Nanoparticle-based Therapeutics: A Review.

PubMed

Han, Qingqing; Niu, Meng; Wu, Qirun; Zhong, Hongshan

2018-01-01

With the development of nanomaterials, nanoparticle-based therapeutics have found increasing application in various fields, including clinical and basic medicine. Real-time monitoring of nanoparticle-based therapeutics is considered critical to both pharmacology and pharmacokinetics. In this review, we discuss the different methods of real-time monitoring of nanoparticle-based therapeutics comprising different types of nanoparticle carriers, such as metal nanoparticles, inorganic nonmetallic nanoparticles, biodegradable polymer nanoparticles, and biological nanoparticles. In the light of examples and analyses, we conclude that the methods of analysis of the four types of nanoparticle carriers are commonly used methods and mostly not necessary. Under most circumstances, real-time monitoring differs according to nanoparticle type, drugs, diseases, and surroundings. With technology development and advanced researches, there have been increasing measures to track the real-time changes in nanoparticles, and this has led to great progress in pharmacology and therapeutics. However, future studies are warranted to determine the accuracy, applicability, and practicability of different technologies. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.

Pharmacological and therapeutic directions in ADHD: Specificity in the PFC.

PubMed

Levy, Florence

2008-02-28

Recent directions in the treatment of ADHD have involved both a broadening of pharmacological perspectives to include nor-adrenergic as well as dopaminergic agents. A review of animal and human studies of pharmacological and therapeutic directions in ADHD suggests that the D1 receptor is a specific site for dopaminergic regulation of the PFC, but optimal levels of dopamine (DA) are required for beneficial effects on working memory. Animal and human studies indicate that the alpha-2A receptor is also important for prefrontal regulation, leaving open the question of the relative importance of these receptor sites. The therapeutic effects of ADHD medications in the prefrontal cortex have focused attention on the development of working memory capacity in ADHD. The actions of dopaminergic vs noradrenergic agents, currently available for the treatment of ADHD have overlapping, but different actions in the prefrontal cortex (PFC) and subcortical centers. While stimulants act on D1 receptors in the dorsolateral prefrontal cortex, they also have effects on D2 receptors in the corpus striatum and may also have serotonergic effects at orbitofrontal areas. At therapeutic levels, dopamine (DA) stimulation (through DAT transporter inhibition) decreases noise level acting on subcortical D2 receptors, while NE stimulation (through alpha-2A agonists) increases signal by acting preferentially in the PFC possibly on DAD1 receptors. On the other hand, alpha-2A noradrenergic transmission is more limited to the prefrontal cortex (PFC), and thus less likely to have motor or stereotypic side effects, while alpha-2B and alpha-2C agonists may have wider cortical effects. The data suggest a possible hierarchy of specificity in the current medications used in the treatment of ADHD, with guanfacine likely to be most specific for the treatment of prefrontal attentional and working memory deficits. Stimulants may have broader effects on both vigilance and motor impulsivity, depending on dose

Soft Polymers for Building up Small and Smallest Blood Supplying Systems by Stereolithography

PubMed Central

Meyer, Wolfdietrich; Engelhardt, Sascha; Novosel, Esther; Elling, Burkhard; Wegener, Michael; Krüger, Hartmut

2012-01-01

Synthesis of a homologous series of photo-polymerizable α,ω-polytetrahydrofuranether-diacrylate (PTHF-DA) resins is described with characterization by NMR, GPC, DSC, soaking and rheometrical measurements. The curing speeds of the resins are determined under UV light exposure. Young’s modulus and tensile strength of fully cured resins show flexible to soft material attributes dependent on the molar mass of the used linear PTHF-diacrylates. Structuring the materials by stereo lithography (SL) and multiphoton polymerization (MPP) leads to tubes and bifurcated tube systems with a diameter smaller than 2 mm aimed at small to smallest supplying systems with capillary dimensions. WST-1 biocompatibility tests ofm polymer extracts show nontoxic characteristics of the adapted polymers after a washing process. Some polymers show shape memory effect (SME). PMID:24955530

Memory Device and Nanofabrication Techniques Using Electrically Configurable Materials

NASA Astrophysics Data System (ADS)

Ascenso Simões, Bruno

Development of novel nanofabrication techniques and single-walled carbon nanotubes field configurable transistor (SWCNT-FCT) memory devices using electrically configurable materials is presented. A novel lithographic technique, electric lithography (EL), that uses electric field for pattern generation has been demonstrated. It can be used for patterning of biomolecules on a polymer surface and patterning of resist as well. Using electrical resist composed of a polymer having Boc protected amine group and iodonium salt, Boc group on the surface of polymer was modified to free amine by applying an electric field. On the modified surface of the polymer, Streptavidin pattern was fabricated with a sub-micron scale. Also patterning of polymer resin composed of epoxy monomers and diaryl iodonium salt by EL has been demonstrated. Reaction mechanism for electric resist configuration is believed to be induced by an acid generation via electrochemical reduction in the resist. We show a novel field configurable transistor (FCT) based on single-walled carbon nanotube network field-effect transistors in which poly (ethylene glycol) crosslinked by electron-beam is incorporated into the gate. The device conductance can be configured to arbitrary states reversibly and repeatedly by applying external gate voltages. Raman spectroscopy revealed that evolution of the ratio of D- to G-band intensity in the SWCNTs of the FCT progressively increases as the device is configured to lower conductance states. Electron transport studies at low temperatures showed a strong temperature dependence of the resistance. Band gap widening of CNTs up to ˜ 4 eV has been observed by examining the differential conductance-gate voltage-bias voltage relationship. The switching mechanism of the FCT is attributed a structural transformation of CNTs via reversible hydrogenation and dehydrogenations induced by gate voltages, which tunes the CNT bandgap continuously and reversibly to non-volatile analog values

A Vertical Organic Transistor Architecture for Fast Nonvolatile Memory.

PubMed

She, Xiao-Jian; Gustafsson, David; Sirringhaus, Henning

2017-02-01

A new device architecture for fast organic transistor memory is developed, based on a vertical organic transistor configuration incorporating high-performance ambipolar conjugated polymers and unipolar small molecules as the transport layers, to achieve reliable and fast programming and erasing of the threshold voltage shift in less than 200 ns. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

(-)Epigallocatechin-3-gallate decreases the stress-induced impairment of learning and memory in rats.

PubMed

Soung, Hung-Sheng; Wang, Mao-Hsien; Tseng, Hsiang-Chien; Fang, Hsu-Wei; Chang, Kuo-Chi

2015-08-18

Stress induces reactive oxygen species (ROS) and causes alterations in brain cytoarchitecture and cognition. Green tea has potent antioxidative properties especially the tea catechin (-) epigallocatechin-3-gallate (EGCG). These powerful antioxidative properties are able to protect against various oxidative damages. In this study we investigated the impact of stress on rats' locomotor activity, learning and memory. Many tea catechins, including EGCG, were examined for their possible therapeutic effects in treating stress-induced impairment. Our results indicated that locomotor activity was decreased, and the learning and memory were impaired in stressed rats (SRs). EGCG treatment was able to prevent the decreased locomotor activity as well as improve the learning and memory in SRs. EGCG treatment was also able to reduce the increased oxidative status in SRs' hippocampi. The above results suggest a therapeutic effect of EGCG in treating stress-induced impairment of learning and memory, most likely by means of its powerful antioxidative properties. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Ocular Pharmacokinetic Study Using T1 Mapping and Gd-Chelate-Labeled Polymers

PubMed Central

Shi, Xianfeng; Liu, Xin; Wu, Xueming; Lu, Zheng-Rong; Li, S. Kevin

2011-01-01

Purpose Recent advances in drug discovery have led to the development of a number of therapeutic macromolecules for treatment of posterior eye diseases. We aimed to investigate the clearance of macromolecular contrast probes (polymers conjugated with Gd-chelate) in the vitreous after intravitreal injections with the recently developed ms-DSEPI-T12 MRI and to examine the degradation of disulfide-containing biodegradable polymers in the vitreous humor in vivo. Methods Intravitreal injections of model contrast agents poly[N-(2-hydroxypropyl)methacrylamide]-GG-1,6-hexanediamine-(Gd-DO3A), biodegradable (Gd-DTPA)-cystine copolymers, and MultiHance were performed in rabbits; their distribution and elimination from the vitreous after injections were determined by MRI. Results Times for macromolecular contrast agents to decrease to half their initial concentrations in the vitreous ranged from 0.4–1.3 days post-injection. Non-biodegradable polymers demonstrated slower vitreal clearance than those of disulfide-biodegradable polymers. Biodegradable polymers had similar clearance as MultiHance. Conclusions Usefulness of T1 mapping and ms-DSEPI-T12 MRI to study ocular pharmacokinetics was demonstrated. Results suggest an enzymatic degradation mechanism for the disulfide linkage in polymers in the vitreous leading to breakup of polymers in vitreous humor over time. PMID:21691891

A Cationic Polymer That Shows High Antifungal Activity against Diverse Human Pathogens.

PubMed

Rank, Leslie A; Walsh, Naomi M; Liu, Runhui; Lim, Fang Yun; Bok, Jin Woo; Huang, Mingwei; Keller, Nancy P; Gellman, Samuel H; Hull, Christina M

2017-10-01

Invasive fungal diseases are generally difficult to treat and often fatal. The therapeutic agents available to treat fungi are limited, and there is a critical need for new agents to combat these deadly infections. Antifungal compound development has been hindered by the challenge of creating agents that are highly active against fungal pathogens but not toxic to the host. Host defense peptides (HDPs) are produced by eukaryotes as a component of the innate immune response to pathogens and have served as inspiration for the development of many new antibacterial compounds. HDP mimics, however, have largely failed to exhibit potent and selective antifungal activity. Here, we present an HDP-like nylon-3 copolymer that is effective against diverse fungi while displaying only mild to moderate toxicity toward mammalian cells. This polymer is active on its own and in synergy with existing antifungal drugs against multiple species of Candida and Cryptococcus , reaching levels of efficacy comparable to those of the clinical agents amphotericin B and fluconazole in some cases. In addition, the polymer acts synergistically with azoles against different species of Aspergillus , including some azole-resistant strains. These findings indicate that nylon-3 polymers are a promising lead for development of new antifungal therapeutic strategies. Copyright © 2017 American Society for Microbiology.

Star polymer-based unimolecular micelles and their application in bio-imaging and diagnosis.

PubMed

Jin, Xin; Sun, Pei; Tong, Gangsheng; Zhu, Xinyuan

2018-02-03

As a novel kind of polymer with covalently linked core-shell structure, star polymers behave in nanostructure in aqueous medium at all concentration range, as unimolecular micelles at high dilution condition and multi-micelle aggregates in other situations. The unique morphologies endow star polymers with excellent stability and functions, making them a promising platform for bio-application. A variety of functions including imaging and therapeutics can be achieved through rational structure design of star polymers, and the existence of plentiful end-groups on shell offers the opportunity for further modification. In the last decades, star polymers have become an attracting platform on fabrication of novel nano-systems for bio-imaging and diagnosis. Focusing on the specific topology and physicochemical properties of star polymers, we have reviewed recent development of star polymer-based unimolecular micelles and their bio-application in imaging and diagnosis. The main content of this review summarizes the synthesis of integrated architecture of star polymers and their self-assembly behavior in aqueous medium, focusing especially on the recent advances on their bio-imaging application and diagnosis use. Finally, we conclude with remarks and give some outlooks for further exploration in this field. Copyright © 2018 Elsevier Ltd. All rights reserved.

Tumor targeting RGD conjugated bio-reducible polymer for VEGF siRNA expressing plasmid delivery

PubMed Central

Kim, Hyun Ah; Nam, Kihoon; Kim, Sung Wan

2014-01-01

Targeted delivery of therapeutic genes to the tumor site is critical for successful and safe cancer gene therapy. The arginine grafted bio-reducible poly (cystamine bisacrylamide-diaminohexane, CBA-DAH) polymer (ABP) conjugated poly (amido amine) (PAMAM), PAM-ABP (PA) was designed previously as an efficient gene delivery carrier. To achieve high efficacy in cancer selective delivery, we developed the tumor targeting bio-reducible polymer, PA-PEG1k-RGD, by conjugating cyclic RGDfC (RGD) peptides, which bind αvβ3/5 integrins, to the PAM-ABP using polyethylene glycol (PEG,1kDa) as a spacer. Physical characterization showed nanocomplex formation with bio-reducible properties between PA-PEG1k-RGD and plasmid DNA (pDNA). In transfection assays, PA-PEG1k-RGD showed significantly higher transfection efficiency in comparison with PAM-ABP or PA-PEG1k-RGD in αvβ3/5 positive MCF7 breast cancer and PANC-1 pancreatic cancer cells. The targeting ability of PA-PEG1k-RGD was further established using a competition assay. To confirm the therapeutic effect, the VEGF siRNA expressing plasmid was constructed and then delivered into cancer cells using PA-PEG1k-RGD. PA-PEG1k-RGD showed 20-59% higher cellular uptake rate into MCF7 and PANC-1 than that of non-targeted polymers. In addition, MCF7 and PANC-1 cancer cells transfected with PA-PEG1k-RGD/pshVEGF complexes had significantly decreased VEGF gene expression (51-71%) and cancer cell viability (35-43%) compared with control. These results demonstrate that a tumor targeting bio-reducible polymer with an anti-angiogenic therapeutic gene could be used for efficient and safe cancer gene therapy. PMID:24894645

Polymersome Carriers: from Self-Assembly to siRNA and Protein Therapeutics

PubMed Central

Christian, David A.; Cai, Shenshen; Bowen, Diana M.; Kim, Younghoon; Pajerowski, J. David; Discher, Dennis E.

2009-01-01

Polymersomes are polymer-based vesicular shells that form upon hydration of amphiphilic block copolymers. These high molecular weight amphiphiles impart physicochemical properties that allow polymersomes to stably encapsulate or integrate a broad range of active molecules. This robustness together with recently described mechanisms for controlled breakdown of degradable polymersomes as well as escape from endolysosomes suggests that polymersomes might be usefully viewed as having structure/property/function relationships somewhere between lipid vesicles and viral capsids. Here we summarize the assembly and development of controlled release polymersomes to encapsulate therapeutics ranging from small molecule anti-cancer drugs to siRNA and therapeutic proteins. PMID:18977437

The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers

NASA Astrophysics Data System (ADS)

Hearon, Keith; Smith, Sarah E.; Maher, Cameron A.; Wilson, Thomas S.; Maitland, Duncan J.

2013-02-01

The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities—that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because the thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150 °C for up to 5 h or to 125 °C for up to 24 h if stabilized with 10,000 ppm BQ and could also be heated to 125 °C for up to 5 h if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization of

The effect of free radical inhibitor on the sensitized radiation crosslinking and thermal processing stabilization of polyurethane shape memory polymers.

PubMed

Hearon, Keith; Smith, Sarah E; Maher, Cameron A; Wilson, Thomas S; Maitland, Duncan J

2013-02-01

The effects of free radical inhibitor on the electron beam crosslinking and thermal processing stabilization of novel radiation crosslinkable polyurethane shape memory polymers (SMPs) blended with acrylic radiation sensitizers have been determined. The SMPs in this study possess novel processing capabilities-that is, the ability to be melt processed into complex geometries as thermoplastics and crosslinked in a secondary step using electron beam irradiation. To increase susceptibility to radiation crosslinking, the radiation sensitizer pentaerythritol triacrylate (PETA) was solution blended with thermoplastic polyurethane SMPs made from 2-butene-1,4-diol and trimethylhexamethylene diisocyanate (TMHDI). Because thermoplastic melt processing methods such as injection molding are often carried out at elevated temperatures, sensitizer thermal instability is a major processing concern. Free radical inhibitor can be added to provide thermal stabilization; however, inhibitor can also undesirably inhibit radiation crosslinking. In this study, we quantified both the thermal stabilization and radiation crosslinking inhibition effects of the inhibitor 1,4-benzoquinone (BQ) on polyurethane SMPs blended with PETA. Sol/gel analysis of irradiated samples showed that the inhibitor had little to no inverse effects on gel fraction at concentrations of 0-10,000 ppm, and dynamic mechanical analysis showed only a slight negative correlation between BQ composition and rubbery modulus. The 1,4-benzoquinone was also highly effective in thermally stabilizing the acrylic sensitizers. The polymer blends could be heated to 150°C for up to five hours or to 125°C for up to 24 hours if stabilized with 10,000 ppm BQ and could also be heated to 125°C for up to 5 hours if stabilized with 1000 ppm BQ without sensitizer reaction occurring. We believe this study provides significant insight into methods for manipulation of the competing mechanisms of radiation crosslinking and thermal stabilization

Probing molecular interactions of poly(styrene-co-maleic acid) with lipid matrix models to interpret the therapeutic potential of the co-polymer.

PubMed

Banerjee, Shubhadeep; Pal, Tapan K; Guha, Sujoy K

2012-03-01

To understand and maximize the therapeutic potential of poly(styrene-co-maleic acid) (SMA), a synthetic, pharmacologically-active co-polymer, its effect on conformation, phase behavior and stability of lipid matrix models of cell membranes were investigated. The modes of interaction between SMA and lipid molecules were also studied. While, attenuated total reflection-Fourier-transform infrared (ATR-FTIR) and static (31)P nuclear magnetic resonance (NMR) experiments detected SMA-induced conformational changes in the headgroup region, differential scanning calorimetry (DSC) studies revealed thermotropic phase behavior changes of the membranes. (1)H NMR results indicated weak immobilization of SMA within the bilayers. Molecular interpretation of the results indicated the role of hydrogen-bond formation and hydrophobic forces between SMA and zwitterionic phospholipid bilayers. The extent of membrane fluidization and generation of isotropic phases were affected by the surface charge of the liposomes, and hence suggested the role of electrostatic interactions between SMA and charged lipid headgroups. SMA was thus found to directly affect the structural integrity of model membranes. Copyright © 2011 Elsevier B.V. All rights reserved.

Effectiveness of Therapeutic Programs for Students with ADHD with Executive Function Deficits

ERIC Educational Resources Information Center

Chaimaha, Napalai; Sriphetcharawut, Sarinya; Lersilp, Suchitporn; Chinchai, Supaporn

2017-01-01

The purpose of this study was to investigate the effectiveness of therapeutic programs, an executive function training program and a collaborative program, for students with attention-deficit/hyperactivity disorder (ADHD) with executive function deficits (EFDs), especially regarding working memory, planning, and monitoring. The participants were…

Release of bioactive peptides from polyurethane films in vitro and in vivo: Effect of polymer composition.

PubMed

Zhang, Jing; Woodruff, Trent M; Clark, Richard J; Martin, Darren J; Minchin, Rodney F

2016-09-01

Thermoplastic polyurethanes (TPUs) are widely used in biomedical applications due to their excellent biocompatibility. Their role as matrices for the delivery of small molecule therapeutics has been widely reported. However, very little is known about the release of bioactive peptides from this class of polymers. Here, we report the release of linear and cyclic peptides from TPUs with different hard and soft segments. Solvent casting of the TPU at room temperature mixed with the different peptides resulted in reproducible efflux profiles with no evidence of drug degradation. Peptide release was dependent on the size as well as the composition of the TPU. Tecoflex 80A (T80A) showed more extensive release than ElastEon 5-325, which correlated with a degree of hydration. It was also shown that the composition of the medium influenced the rate and extent of peptide efflux. Blending the different TPUs allowed for better control of peptide efflux, especially the initial burst effect. Peptide-loaded TPU prolonged the plasma levels of the anti-inflammatory cyclic peptide PMX53, which normally has a plasma half-life of less than 30min. Using a blend of T80A and E5-325, therapeutic plasma levels of PMX53 were observed up to 9days following a single intraperitoneal implantation of the drug-loaded film. PMX53 released from the blended TPUs significantly inhibited B16-F10 melanoma tumor growth in mice demonstrating its bioactivity in vivo. This study provides important findings for TPU-based therapeutic peptide delivery that could improve the pharmacological utility of peptides as therapeutics. Therapeutic peptides can be highly specific and potent pharmacological agents, but are poorly absorbed and rapidly degraded in the body. This can be overcome by using a matrix that protects the peptide in vivo and promotes its slow release so that a therapeutic effect can be achieved over days or weeks. Thermoplastic polyurethanes are a versatile family of polymers that are biocompatible

Polymer based drug delivery systems for mycobacterial infections.

PubMed

Pandey, Rajesh; Khuller, G K

2004-07-01

In the last decade, polymer based technologies have found wide biomedical applications. Polymers, whether synthetic (e.g. polylactide-co-glycolide or PLG) or natural (e.g. alginate, chitosan etc.), have the property of encapsulating a diverse range of molecules of biological interest and bear distinct therapeutic advantages such as controlled release of drugs, protection against the premature degradation of drugs and reduction in drug toxicity. These are important considerations in the long-duration treatment of chronic infectious diseases such as tuberculosis in which patient non-compliance is the major obstacle to successful chemotherapy. Antitubercular drugs, singly or in combination, have been encapsulated in polymers to provide controlled drug release and the system also offers the flexibility of selecting various routes of administration such as oral, subcutaneous and aerosol. The present review highlights the approaches towards the preparation of polymeric antitubercular drug delivery systems, emphasizing how the route of administration may influence drug bioavailability as well as the chemotherapeutic efficacy. In addition, the pros and cons of the various delivery systems are also discussed.

Analysis of intelligent hinged shell structures: deployable deformation and shape memory effect

NASA Astrophysics Data System (ADS)

Shi, Guang-Hui; Yang, Qing-Sheng; He, X. Q.

2013-12-01

Shape memory polymers (SMPs) are a class of intelligent materials with the ability to recover their initial shape from a temporarily fixable state when subjected to external stimuli. In this work, the thermo-mechanical behavior of a deployable SMP-based hinged structure is modeled by the finite element method using a 3D constitutive model with shape memory effect. The influences of hinge structure parameters on the nonlinear loading process are investigated. The total shape memory of the processes the hinged structure goes through, including loading at high temperature, decreasing temperature with load carrying, unloading at low temperature and recovering the initial shape with increasing temperature, are illustrated. Numerical results show that the present constitutive theory and the finite element method can effectively predict the complicated thermo-mechanical deformation behavior and shape memory effect of SMP-based hinged shell structures.

Past, Present, and Future Technologies for Oral Delivery of Therapeutic Proteins

PubMed Central

SINGH, RAJESH; SINGH, SHAILESH; LILLARD, JAMES W.

2015-01-01

Biological drugs are usually complex proteins and cannot be orally delivered due to problems related to degradation in the acidic and protease-rich environment of the gastrointestinal (GI) tract. The high molecular weight of these drugs often results in poor absorption into the periphery when administered orally. The most common route of administration for these therapeutic proteins is injection. Most of these proteins have short serum half-lives and need to be administered frequently or in high doses to be effective. So, difficulties in the administration of protein-based drugs provides the motivation for developing drug delivery systems (DDSs) capable of maintaining therapeutic drug levels without side effects as well as traversing the deleterious mucosal environment. Employing a polymer as an entrapment matrix is a common feature among the different types of systems currently being pursued for protein delivery. Protein release from these matrices can occur through various mechanisms, such as diffusion through or erosion of the polymer matrix, and sometimes a combination of both. Encapsulation of proteins in liposomes has also been a widely investigated technology for protein delivery. All of these systems have merit and our worthy of pursuit. PMID:17918721

Memory-updating abrogates extinction of learned immunosuppression.

PubMed

Hadamitzky, Martin; Bösche, Katharina; Wirth, Timo; Buck, Benjamin; Beetz, Oliver; Christians, Uwe; Schniedewind, Björn; Lückemann, Laura; Güntürkün, Onur; Engler, Harald; Schedlowski, Manfred

2016-02-01

When memories are recalled, they enter a transient labile phase in which they can be impaired or enhanced followed by a new stabilization process termed reconsolidation. It is unknown, however, whether reconsolidation is restricted to neurocognitive processes such as fear memories or can be extended to peripheral physiological functions as well. Here, we show in a paradigm of behaviorally conditioned taste aversion in rats memory-updating in learned immunosuppression. The administration of sub-therapeutic doses of the immunosuppressant cyclosporin A together with the conditioned stimulus (CS/saccharin) during retrieval blocked extinction of conditioned taste aversion and learned suppression of T cell cytokine (interleukin-2; interferon-γ) production. This conditioned immunosuppression is of clinical relevance since it significantly prolonged the survival time of heterotopically transplanted heart allografts in rats. Collectively, these findings demonstrate that memories can be updated on both neural and behavioral levels as well as on the level of peripheral physiological systems such as immune functioning. Copyright © 2015 Elsevier Inc. All rights reserved.

Protein Phosphatase-1 Inhibitor-2 Is a Novel Memory Suppressor.

PubMed

Yang, Hongtian; Hou, Hailong; Pahng, Amanda; Gu, Hua; Nairn, Angus C; Tang, Ya-Ping; Colombo, Paul J; Xia, Houhui