shivaprasad manchineella - Academia.edu (original) (raw)

Papers by shivaprasad manchineella

Research paper thumbnail of CHAPTER 13. Stimuli-responsive Material Inspired Drug Delivery Systems and Devices

Biomaterials Science Series, 2018

Stimuli-responsive materials, owing to the fascinating feature of the controlled release of the p... more Stimuli-responsive materials, owing to the fascinating feature of the controlled release of the payload, have been actively researched to develop smart materials systems and devices for drug delivery applications. Such devices could be controlled using a variety of physical, chemical and biological stimuli such as temperature, electric field, ultrasound, magnetic field, pH, ionic strength, enzymes, endogenous chemical molecules and receptors, and thus provide control over the temporal release of the drug. This chapter summarises the various aspects of such materials inspired systems and devices, and introduces their application in the field of drug delivery and therapeutics.

Research paper thumbnail of Development of Biomolecule Integrated Materials and their Biological Applications

Advances in the Chemistry and Physics of Materials, 2019

Research paper thumbnail of Melanin incorporated electroactive and antioxidant silk fibroin nanofibrous scaffolds for nerve tissue engineering

Materials science & engineering. C, Materials for biological applications, 2019

Nerve restoration and repair in the central nervous system is complicated and requires several fa... more Nerve restoration and repair in the central nervous system is complicated and requires several factors to be considered while designing the scaffolds like being bioactive as well as having neuroinductive, neuroconductive and antioxidant properties. Aligned electrospun nanofibers provide necessary guidance and topographical cues required for directing the axonal and neurite outgrowth during regeneration. Conduction of nerve impulses is a mandatory feature of a typical nerve. The neuro-conductive property can be imparted by blending the biodegradable, bioactive polymers with conductive polymers. This will provide additional features, i.e., electrical cues to the already existing topographical and bioactive cues in order to make it a more multifaceted neuroregenerative approach. Hence in the present study, we used a combination of silk fibroin and melanin for the fabrication of random and aligned electrospun nanofibrous composite scaffolds. We performed the physico-chemical characteriz...

Research paper thumbnail of Cyclic Dipeptide-Based Ambidextrous Supergelators: Minimalistic Rational Design, Structure-Gelation Studies, and In Situ Hydrogelation

Research paper thumbnail of Radical-Scavenging Antioxidant Cyclic Dipeptides and Silk Fibroin Biomaterials

European Journal of Organic Chemistry, 2017

Cyclic dipeptide (CDP) based radical-scavenging antioxidant molecules have been developed through... more Cyclic dipeptide (CDP) based radical-scavenging antioxidant molecules have been developed through structure-activity screening of rationally designed symmetric and asymmetric aromatic molecules. The antioxidant efficiencies of the designed CDPs were evaluated against the standard antioxidants ascorbic acid (natural) and butylated hydroxyanisole (a synthetic ingredient used in food, cosmetics, and medicine). Incorporation of the non-proteinogenic aromatic amino acid L-3,4dihydroxyphenylalanine (DOPA) into the structure bestowed the CDPs with superior antioxidant properties. Detailed colorimetric antioxidant studies demonstrated the potential radical-scaveng-[a]

Research paper thumbnail of Surface-Functionalized Silk Fibroin Films as a Platform To Guide Neuron-like Differentiation of Human Mesenchymal Stem Cells

ACS applied materials & interfaces, Jan 7, 2016

Surface interactions at the biomaterial-cellular interface determine the proliferation and differ... more Surface interactions at the biomaterial-cellular interface determine the proliferation and differentiation of stem cells. Manipulating such interactions through the surface chemistry of scaffolds renders control over directed stem cell differentiation into the cell lineage of interest. This approach is of central importance for stem cell-based tissue engineering and regenerative therapy applications. In the present study, silk fibroin films (SFFs) decorated with integrin-binding laminin peptide motifs (YIGSR and GYIGSR) were prepared and employed for in vitro adult stem cell-based neural tissue engineering applications. Functionalization of SFFs with short peptides showcased the peptide sequence and nature of functionalization-dependent differentiation of bone marrow-derived human mesenchymal stem cells (hMSCs). Intriguingly, covalently functionalized SFFs with GYIGSR hexapeptide (CL2-SFF) supported hMSC proliferation and maintenance in an undifferentiated pluripotent state and dire...

Research paper thumbnail of Molecular Self-Assembly of Cyclic Dipeptide Derivatives and Their Applications

ChemPlusChem, 2016

Cyclic dipeptides (CDPs) are heterocyclic 2,5-diketopiperazines with exceptional structural rigid... more Cyclic dipeptides (CDPs) are heterocyclic 2,5-diketopiperazines with exceptional structural rigidity, enzymatic stability, and biological activity, exhibiting a substantial tendency for intermolecular interactions. The strong intermolecular interactions driven by unique hydrogen bonding patterns render CDPs with a high propensity to undergo molecular ChemPlusChem 10.

Research paper thumbnail of Pigmented Silk Nanofibrous Composite for Skeletal Muscle Tissue Engineering

Advanced Healthcare Materials, 2016

Skeletal muscle tissue engineering (SMTE) employs designed biomaterial scaffolds for promoting my... more Skeletal muscle tissue engineering (SMTE) employs designed biomaterial scaffolds for promoting myogenic differentiation of myoblasts to functional myotubes. Oxidative stress plays a significant role in the biocompatibility of biomaterials as well as in the fate of myoblasts during myogenesis and is also associated with pathological conditions such as myotonic dystrophy. The inherent electrical excitability of muscle cells inspired the use of electroactive scaffolds for SMTE. Conducting polymers attracted the attention of researchers for their use in muscle tissue engineering. However, poor biocompatibility, biodegradability and development of oxidative stress associated immunogenic response limits the extensive use of synthetic conducting polymers for SMTE. In order to address the limitations of synthetic polymers, intrinsically electroactive and antioxidant silk fibroin/melanin composite films and electrospun fiber mats were fabricated and evaluated as scaffolds for promoting myogenesis in vitro. Melanin incorporation modulated the thermal stability, electrical conductivity of scaffolds, fiber alignment in electrospun mats and imparted good antioxidant properties to the scaffolds. The composite electrospun scaffolds promoted myoblast assembly and differentiation into uniformly aligned high aspect ratio myotubes. The results highlight the significance of scaffold topography along with conductivity in promoting myogenesis and the potential application of silk nanofibrous composite as electoractive platform for SMTE.

Research paper thumbnail of Hydrogen bond directed self-assembly of cyclic dipeptide derivatives: gelation and ordered hierarchical architectures

Research paper thumbnail of Rhodamine based bright red colourimetric and turn-on fluorescence chemosensor for selective detection of Cu2+

Materials Technology, 2011

Copper is one of the essential trace nutrients in biological systems. Apart from its biological r... more Copper is one of the essential trace nutrients in biological systems. Apart from its biological role, copper is predominantly being used in ceramics, alloys, household utensils, electrical wires, fertiliser preparation and in various engineering purposes, owing to its high malleability, electrical conductivity and antibacterial activity. Such widespread use leads to accumulation of copper in the environment, which subsequently gets into the human body. Therefore, environmental and biological detection of copper is necessary to assess its concentration levels. We have developed 4-(diethylamino)-salicylaldehyde rhodamine hydrazone ligand 1 as a naked eye chemosensor for Cu 2z with enhanced turn-on fluorescence emission in the longer wavelength region that works even in aqueous media. The observed turn-on colourimetric and fluorescence emission upon binding of ligand 1 to Cu 2z was attributed to the ring opening of spirolactam moiety and the strong coordination ability of ring opened form to the copper(II) ion. Ligand 1 can be readily used for the environmental as well as biological detection of Cu 2z , owing to excitation and fluorescence emission in the longer wavelength region, vomiting adverse effects of ultraviolet radiation as observed with most of the reported chemosensors for Cu 2z .

Research paper thumbnail of Solvent‐Induced Helical Assembly and Reversible Chiroptical Switching of Chiral Cyclic‐Dipeptide‐Functionalized Naphthalenediimides

Chemistry – A European Journal, 2013

FULL PAPER extremely useful molecular platform with applications ranging from organic electronics... more FULL PAPER extremely useful molecular platform with applications ranging from organic electronics to biomedicine. [12] The possibility of selective imide functionalization, high p-acidity, planarity conducive to strong p-p interactions, and ease of pro-A C H T U N G T R E N N U N G cessability of these systems in solution has led to increased demand for the design of novel NDI-based supramolecular systems. Imide substituents studied have included alkyl chains, aromatic rings, amino acids, dipeptides, and a combination of alkyl chains and amino acids. [13-21] Our recent work demonstrated the potential of a biomimetic strategy based on amino acid-and peptide-functionalized NDIs for designing 0D, 1D, and 2D molecular materials with interesting structural and functional properties. [12e, 20, 21] The functional relevance of these biomimetic molecular materials varied from attolitre containers for miniaturized biological assays to organic electronics to self-cleaning functional molecular materials. [12e, 20] Furthermore, the amino acid-and dipeptidefunctionalized NDIs emphasized the significance of the chiral centre of the amino acid directly attached to the imide nitrogen in controlling the supramolecular helical chirality of the derived self-assembled structures. [21] Subsequently, the chiroptical properties of these systems revealed significant chiral transcription, amplification, and retentive helical memory with probable implications for the origin of homochirality in Nature. [1c] Cyclic dipeptides (CDPs) are the smallest possible cyclic forms of peptides and are known for their unique structural properties and diverse biological functions. [22] By virtue of their structural rigidity, propensity for strong intermolecular hydrogen bonding, molecular recognition, and resistance towards proteolytic enzymes, CDPs constitute good supramolecular synthons for the preparation of soft organogels, hydrogels, and well-defined nanoarchitectures for various applications. [23-25] We envisaged an inclusive molecular design based on NDI with CDP chiral auxiliaries as monomers for the noncovalent synthesis of helical supramolecular polymers. The NDI-CDP (NCDP) conjugates serve as model systems to evaluate the role of chiral centres on the imide substituents located several atoms away from the imide nitrogen in inducing specific helical assemblies of NDI. This study complements our earlier work, in which the chiral centre of the first amino acid directly attached as the imide substituent through the a-amino group was found to determine the outcome of the helical assembly of NDIs. [20, 21] The NCDP molecular platform has also assisted our understanding of the influence of a-substituents and the corresponding chiral centres in CDP auxiliaries. Herein, we report novel symmetrical NCDPs (1-6) as new molecular platforms to engineer NDI chiral assembly through aromatic (NDI) and hydrogen-bonding (CDP) interactions. Furthermore, this study emphasizes the significance of chiral auxiliaries and the decisive role played by solvent composition in modulating the helical supramolecular self-assembly of such systems.

Research paper thumbnail of Biomolecules-derived biomaterials

Biomaterials, 2019

Human civilization has witnessed the use of materials-derived from biomolecules of plants and ani... more Human civilization has witnessed the use of materials-derived from biomolecules of plants and animal origin for biomedical applications since ancient era. In recent years, precision design principles have been adopted to develop novel biomaterials derived from biomolecules. The biomolecules-derived biomaterials fabrication is dependent on chemical, biochemical and mechanical parameters of biomolecules and their bulk materials. Thus, structural variations and weak noncovalent interactions present within the basic building blocks greatly influence the functional features and applications. This comprehensive review provides one-stop information on recent innovations of various biomaterial-types derived from a diverse class of biomolecules through selected and representative examples with potential biomedical applications ranging from diagnosis, biosensing, antimicrobial efficacy, anticancer therapeutics, drug delivery, bioprinting, bioimaging, tissue engineering and regenerative medicine. The discussion systematically follows the top-down approach in the order of molecular complexity viz., biomacromolecules, oligomers and monomers of all classes of biomolecules (proteins, nucleic acids, carbohydrates and lipids) including a special section on biohybrid materials derived from molecular systems integrated with more than one class of biomolecules. In addition to providing overview of impressive advancements in the area, synergistic integration of biomolecules with synthetic materials to develop smart biomaterials is emphasized to improve the chemical, mechanical, stimuli-responsiveness, immunogenicity and biocompatibility features.

Research paper thumbnail of CHAPTER 13. Stimuli-responsive Material Inspired Drug Delivery Systems and Devices

Biomaterials Science Series, 2018

Stimuli-responsive materials, owing to the fascinating feature of the controlled release of the p... more Stimuli-responsive materials, owing to the fascinating feature of the controlled release of the payload, have been actively researched to develop smart materials systems and devices for drug delivery applications. Such devices could be controlled using a variety of physical, chemical and biological stimuli such as temperature, electric field, ultrasound, magnetic field, pH, ionic strength, enzymes, endogenous chemical molecules and receptors, and thus provide control over the temporal release of the drug. This chapter summarises the various aspects of such materials inspired systems and devices, and introduces their application in the field of drug delivery and therapeutics.

Research paper thumbnail of Development of Biomolecule Integrated Materials and their Biological Applications

Advances in the Chemistry and Physics of Materials, 2019

Research paper thumbnail of Melanin incorporated electroactive and antioxidant silk fibroin nanofibrous scaffolds for nerve tissue engineering

Materials science & engineering. C, Materials for biological applications, 2019

Nerve restoration and repair in the central nervous system is complicated and requires several fa... more Nerve restoration and repair in the central nervous system is complicated and requires several factors to be considered while designing the scaffolds like being bioactive as well as having neuroinductive, neuroconductive and antioxidant properties. Aligned electrospun nanofibers provide necessary guidance and topographical cues required for directing the axonal and neurite outgrowth during regeneration. Conduction of nerve impulses is a mandatory feature of a typical nerve. The neuro-conductive property can be imparted by blending the biodegradable, bioactive polymers with conductive polymers. This will provide additional features, i.e., electrical cues to the already existing topographical and bioactive cues in order to make it a more multifaceted neuroregenerative approach. Hence in the present study, we used a combination of silk fibroin and melanin for the fabrication of random and aligned electrospun nanofibrous composite scaffolds. We performed the physico-chemical characteriz...

Research paper thumbnail of Cyclic Dipeptide-Based Ambidextrous Supergelators: Minimalistic Rational Design, Structure-Gelation Studies, and In Situ Hydrogelation

Research paper thumbnail of Radical-Scavenging Antioxidant Cyclic Dipeptides and Silk Fibroin Biomaterials

European Journal of Organic Chemistry, 2017

Cyclic dipeptide (CDP) based radical-scavenging antioxidant molecules have been developed through... more Cyclic dipeptide (CDP) based radical-scavenging antioxidant molecules have been developed through structure-activity screening of rationally designed symmetric and asymmetric aromatic molecules. The antioxidant efficiencies of the designed CDPs were evaluated against the standard antioxidants ascorbic acid (natural) and butylated hydroxyanisole (a synthetic ingredient used in food, cosmetics, and medicine). Incorporation of the non-proteinogenic aromatic amino acid L-3,4dihydroxyphenylalanine (DOPA) into the structure bestowed the CDPs with superior antioxidant properties. Detailed colorimetric antioxidant studies demonstrated the potential radical-scaveng-[a]

Research paper thumbnail of Surface-Functionalized Silk Fibroin Films as a Platform To Guide Neuron-like Differentiation of Human Mesenchymal Stem Cells

ACS applied materials & interfaces, Jan 7, 2016

Surface interactions at the biomaterial-cellular interface determine the proliferation and differ... more Surface interactions at the biomaterial-cellular interface determine the proliferation and differentiation of stem cells. Manipulating such interactions through the surface chemistry of scaffolds renders control over directed stem cell differentiation into the cell lineage of interest. This approach is of central importance for stem cell-based tissue engineering and regenerative therapy applications. In the present study, silk fibroin films (SFFs) decorated with integrin-binding laminin peptide motifs (YIGSR and GYIGSR) were prepared and employed for in vitro adult stem cell-based neural tissue engineering applications. Functionalization of SFFs with short peptides showcased the peptide sequence and nature of functionalization-dependent differentiation of bone marrow-derived human mesenchymal stem cells (hMSCs). Intriguingly, covalently functionalized SFFs with GYIGSR hexapeptide (CL2-SFF) supported hMSC proliferation and maintenance in an undifferentiated pluripotent state and dire...

Research paper thumbnail of Molecular Self-Assembly of Cyclic Dipeptide Derivatives and Their Applications

ChemPlusChem, 2016

Cyclic dipeptides (CDPs) are heterocyclic 2,5-diketopiperazines with exceptional structural rigid... more Cyclic dipeptides (CDPs) are heterocyclic 2,5-diketopiperazines with exceptional structural rigidity, enzymatic stability, and biological activity, exhibiting a substantial tendency for intermolecular interactions. The strong intermolecular interactions driven by unique hydrogen bonding patterns render CDPs with a high propensity to undergo molecular ChemPlusChem 10.

Research paper thumbnail of Pigmented Silk Nanofibrous Composite for Skeletal Muscle Tissue Engineering

Advanced Healthcare Materials, 2016

Skeletal muscle tissue engineering (SMTE) employs designed biomaterial scaffolds for promoting my... more Skeletal muscle tissue engineering (SMTE) employs designed biomaterial scaffolds for promoting myogenic differentiation of myoblasts to functional myotubes. Oxidative stress plays a significant role in the biocompatibility of biomaterials as well as in the fate of myoblasts during myogenesis and is also associated with pathological conditions such as myotonic dystrophy. The inherent electrical excitability of muscle cells inspired the use of electroactive scaffolds for SMTE. Conducting polymers attracted the attention of researchers for their use in muscle tissue engineering. However, poor biocompatibility, biodegradability and development of oxidative stress associated immunogenic response limits the extensive use of synthetic conducting polymers for SMTE. In order to address the limitations of synthetic polymers, intrinsically electroactive and antioxidant silk fibroin/melanin composite films and electrospun fiber mats were fabricated and evaluated as scaffolds for promoting myogenesis in vitro. Melanin incorporation modulated the thermal stability, electrical conductivity of scaffolds, fiber alignment in electrospun mats and imparted good antioxidant properties to the scaffolds. The composite electrospun scaffolds promoted myoblast assembly and differentiation into uniformly aligned high aspect ratio myotubes. The results highlight the significance of scaffold topography along with conductivity in promoting myogenesis and the potential application of silk nanofibrous composite as electoractive platform for SMTE.

Research paper thumbnail of Hydrogen bond directed self-assembly of cyclic dipeptide derivatives: gelation and ordered hierarchical architectures

Research paper thumbnail of Rhodamine based bright red colourimetric and turn-on fluorescence chemosensor for selective detection of Cu2+

Materials Technology, 2011

Copper is one of the essential trace nutrients in biological systems. Apart from its biological r... more Copper is one of the essential trace nutrients in biological systems. Apart from its biological role, copper is predominantly being used in ceramics, alloys, household utensils, electrical wires, fertiliser preparation and in various engineering purposes, owing to its high malleability, electrical conductivity and antibacterial activity. Such widespread use leads to accumulation of copper in the environment, which subsequently gets into the human body. Therefore, environmental and biological detection of copper is necessary to assess its concentration levels. We have developed 4-(diethylamino)-salicylaldehyde rhodamine hydrazone ligand 1 as a naked eye chemosensor for Cu 2z with enhanced turn-on fluorescence emission in the longer wavelength region that works even in aqueous media. The observed turn-on colourimetric and fluorescence emission upon binding of ligand 1 to Cu 2z was attributed to the ring opening of spirolactam moiety and the strong coordination ability of ring opened form to the copper(II) ion. Ligand 1 can be readily used for the environmental as well as biological detection of Cu 2z , owing to excitation and fluorescence emission in the longer wavelength region, vomiting adverse effects of ultraviolet radiation as observed with most of the reported chemosensors for Cu 2z .

Research paper thumbnail of Solvent‐Induced Helical Assembly and Reversible Chiroptical Switching of Chiral Cyclic‐Dipeptide‐Functionalized Naphthalenediimides

Chemistry – A European Journal, 2013

FULL PAPER extremely useful molecular platform with applications ranging from organic electronics... more FULL PAPER extremely useful molecular platform with applications ranging from organic electronics to biomedicine. [12] The possibility of selective imide functionalization, high p-acidity, planarity conducive to strong p-p interactions, and ease of pro-A C H T U N G T R E N N U N G cessability of these systems in solution has led to increased demand for the design of novel NDI-based supramolecular systems. Imide substituents studied have included alkyl chains, aromatic rings, amino acids, dipeptides, and a combination of alkyl chains and amino acids. [13-21] Our recent work demonstrated the potential of a biomimetic strategy based on amino acid-and peptide-functionalized NDIs for designing 0D, 1D, and 2D molecular materials with interesting structural and functional properties. [12e, 20, 21] The functional relevance of these biomimetic molecular materials varied from attolitre containers for miniaturized biological assays to organic electronics to self-cleaning functional molecular materials. [12e, 20] Furthermore, the amino acid-and dipeptidefunctionalized NDIs emphasized the significance of the chiral centre of the amino acid directly attached to the imide nitrogen in controlling the supramolecular helical chirality of the derived self-assembled structures. [21] Subsequently, the chiroptical properties of these systems revealed significant chiral transcription, amplification, and retentive helical memory with probable implications for the origin of homochirality in Nature. [1c] Cyclic dipeptides (CDPs) are the smallest possible cyclic forms of peptides and are known for their unique structural properties and diverse biological functions. [22] By virtue of their structural rigidity, propensity for strong intermolecular hydrogen bonding, molecular recognition, and resistance towards proteolytic enzymes, CDPs constitute good supramolecular synthons for the preparation of soft organogels, hydrogels, and well-defined nanoarchitectures for various applications. [23-25] We envisaged an inclusive molecular design based on NDI with CDP chiral auxiliaries as monomers for the noncovalent synthesis of helical supramolecular polymers. The NDI-CDP (NCDP) conjugates serve as model systems to evaluate the role of chiral centres on the imide substituents located several atoms away from the imide nitrogen in inducing specific helical assemblies of NDI. This study complements our earlier work, in which the chiral centre of the first amino acid directly attached as the imide substituent through the a-amino group was found to determine the outcome of the helical assembly of NDIs. [20, 21] The NCDP molecular platform has also assisted our understanding of the influence of a-substituents and the corresponding chiral centres in CDP auxiliaries. Herein, we report novel symmetrical NCDPs (1-6) as new molecular platforms to engineer NDI chiral assembly through aromatic (NDI) and hydrogen-bonding (CDP) interactions. Furthermore, this study emphasizes the significance of chiral auxiliaries and the decisive role played by solvent composition in modulating the helical supramolecular self-assembly of such systems.

Research paper thumbnail of Biomolecules-derived biomaterials

Biomaterials, 2019

Human civilization has witnessed the use of materials-derived from biomolecules of plants and ani... more Human civilization has witnessed the use of materials-derived from biomolecules of plants and animal origin for biomedical applications since ancient era. In recent years, precision design principles have been adopted to develop novel biomaterials derived from biomolecules. The biomolecules-derived biomaterials fabrication is dependent on chemical, biochemical and mechanical parameters of biomolecules and their bulk materials. Thus, structural variations and weak noncovalent interactions present within the basic building blocks greatly influence the functional features and applications. This comprehensive review provides one-stop information on recent innovations of various biomaterial-types derived from a diverse class of biomolecules through selected and representative examples with potential biomedical applications ranging from diagnosis, biosensing, antimicrobial efficacy, anticancer therapeutics, drug delivery, bioprinting, bioimaging, tissue engineering and regenerative medicine. The discussion systematically follows the top-down approach in the order of molecular complexity viz., biomacromolecules, oligomers and monomers of all classes of biomolecules (proteins, nucleic acids, carbohydrates and lipids) including a special section on biohybrid materials derived from molecular systems integrated with more than one class of biomolecules. In addition to providing overview of impressive advancements in the area, synergistic integration of biomolecules with synthetic materials to develop smart biomaterials is emphasized to improve the chemical, mechanical, stimuli-responsiveness, immunogenicity and biocompatibility features.