Organogels, hydrogels and bigels as transdermal delivery systems for diltiazem hydrochloride

In the present study,gel formulations of organogels,hydrogels,and oleo-hydrogel(bigels)were evaluated as transdermal drug delivery systems for diltiazem HCL(DH).Organogels were prepared using soya-bean oil(SO)as a solvent and span 60(Sp 60),cetyl alcohol(CA)or lecithinpluronic(PLO)as organogelators without and with different surfactants(2%w/w)namely span 80(Sp80),tween 20(T20)and tween 80(T80).On the other hand,hydrogels were formulated using Hydroxypropyl-methylcellulose(HPMC)polymer and bigels were prepared by mixing organogels with HPMC hydrogels.The prepared gels were analyzed microscopically,thermally by DTA and for pH,and viscosity.The effect of gelator used,surfactant types and pH of the sink on DH release from cellophane membrane was investigated.In addition,the DH permeability across the rabbit skin was evaluated.Finally,the in vivo performance of various gel formulationswas assessed based on the hypotensive effects of the drug using hypertensive albino male rat models.The microscopical analysis indicated that the solid fibers formed by gelator particles form the backbone of the organogels while bigels appeared as emulsion like.The addition of surfactants showed an increase in organogel viscosity.The thermal analysis of organogels indicated that the drug present in amorphous not in crystalline form.The release studies indicated that DH release from organogels,hydrogels and bigels could be controlled.The included surfactants decreased the DH release and permeation from organogels compared to those without surfactants using either Sp60 or CA.HPMC hydrogel and Bigels showed higher DH release and permeation rates when compared to organogels.The percent DH released in different pH values was in the following descending order:pH5.5>pH1.2>pH6.8>pH7.4.The in vivo antihypertensive activity of DH using different transdermal gels is arranged as following:hydrogels>PLO organogel>bigel>Sp 60 organogel.

Versatile Organogels of Aluminum Oxide Subnanosheets for Locking Solvents and Adhesion

Herein,we present a facile strategy to prepare versatile aluminum oxide subnanometer nanosheets with oleic acid and stearic acid ligands(OA-Al SNSs and SA-Al SNSs,respectively).The size effect endows subnanosheets with abundant acting sites,remarkable intermolecular interactions,and unique polymer-like properties,including flexibility,viscoelasticity,and sol-gel transitions,which is quite different from traditional inorganic materials.Consequently,subnanosheets could form freestanding organogels and OA-Al SNSs exhibit satisfying semisolidification of various solvents,making it an intriguing candidate for the safe storage and transportation of solvents.Furthermore,SA-Al SNSs exhibit excellent adhesive properties of high strength on diverse substrates,and it is easy to erase it without any damage,demonstrating the promising prospects in practical applications.

Oleophobic interaction mediated slippery organogels with ameliorated mechanical performance and satisfactory fouling-resistance

Owing to their inherent semi-solid property and lubricant ability,organogels manifest various unique characteristics and serve as promising candidates for antifouling.However,the poor mechanical properties of organogels often limit their practical applications.Herein,we report a simple and effective method to prepare organogels with reinforced mechanical performance and surface lubricant ability with the synergistic roles played by oleophobic and oleophilic chains.The rigid oleophobic chains have a poor affinity to lubricating solvent,which gives rise to high oleophobic interactions between polymer networks;the soft oleophilic chains possess a high affinity to the low surface energy solvent,which lead to high solvent content to maintain the satisfactory lubricant capacity.The organogel of oleophobic methyl methacrylate(MMA)and oleophilic lauryl methacrylate(LMA)is chosen as a representative example to illustrate this concept.With the optimal composition,the as-prepared organogels offer satisfactory tensile fracture stress,fracture strain,Young’s modulus,toughness,and tearing fracture energy of 480 k Pa,550%,202 k Pa,1.14 MJ m,and 5.14 k J m,respectively,which are far beyond the classical PLMA organogels.Furthermore,the biofouling resistance tests demonstrate 4 to 9-fold reduction of protein and bacteria adhesion on the reinforced organogels surface in comparison to the glass substrate and solvent-free dry organogels.This simple and effective approach to toughen organogels,we hope,can be applied in various fields with different practical functional requirements in the future.

Intermolecular hydrogen-bond interaction to promote thermoreversible 2'-deoxyuridine-based AIE-organogels

Fluorescent supramolecular nucleoside-based organogels or hydrogels have attracted increasing attention owing to their tunable stability,drug delivery,tissue engineering,and inherent biocompatibility for applications in designing sensors.As the temperature of a constant TPE-Octa-dU gelato r at MGC as low as 0.2 wt%was increased with gel to sol transition,a progressive decrease in the fluorescence intensity was observed.~1 H NMR study in ethanol-d_(6)/H_(2)O revealed the existence of intermolecular hydrogen-bond interaction between uridine nucleobase and triazole moieties.Based on these experiments,thus organogels induced by hydrogen bonding can promote an aggregation-induced emission(AIE)of TPE moiety.Thermoreversible gelation properties have been investigated systematically,including AIE-shapemorphing architecture owing to their unique solid-liquid interface and easy processability.At the same line,the related TPE-EdU derivative which was synthesized from 5-ethynyl-2'-deoxyuridine does not delive r organogels or hydrogels,a nd under similar circumstances TPE moiety of TPE-EdU does not efficiently exhibit AIE phenomenon either.

Direct Evidence for the Effect of Intermolecular Hydrogen Bonding on Organogels

In order to get direct evidence for the effect of intermolecular hydrogen bonding on the organogels, one arnide group in N-（3, 4, 5-octyloxybenzoyl）-N＇-（4＇-aminobenzoyl）hydrazine（D8） was replaced by a Schiff base group, forming N-（3,4,5-octyloxybenzoyl）-N＇-（4＇-amidobenzoyl） acylhydrazone（T8SchA）. D8 and T8SchA organogels in cyclohexane show the same hexagonal columnar structure. And the hydrogen bonding was demonstrated to be still interacting in the organogels. However, although the molecular geometry of D8 was well retained in T8SchA, the molecular dipole moment of T8SchA is bigger than that of D8 due to the reduction of the number of hydrogen bonds. Thus, the decreased gelling stability of T8SchA compared to that of D8 can only be attributed to the reduction of the number of intermolecular hydrogen bonds, which provides direct evidence that intermolecular hydrogen bonding plays an important role in stabilising organogels.

Water-resistant conductive organogels with sensation and actuation functions for artificial neuro-sensory muscular systems

The development of functional flexible conductive materials can significantly contribute to the improvement of intelligent human–computer integration.However,it is a challenge to endow human–machine interface with perception and response actuation simultaneously.Herein,a customizable and multifunctional electronic conductive organogel is proposed by combining conductive carbon nanotube(CNT)clusters and flexible adhesive organogels.The conductive CNT cluster layers generated on the surface of organogels equip the resulting organogel-based conductors with considerable quasi-superhydrophobicity and increase their potential applicability as highly sensitive stress and strain sensors.In particular,this quasi-superhydrophobicity is insensitive to tensile strain.Based on customizable conductive networks and entropy-driven organogel actuation,the conductive organogels can sense various strain and stress signals and imitate natural organisms with muscle actuation and neurofeedback.This strategy for preparing electronic conductors can enhance the rational design of soft robotics and artificial intelligence devices,facilitating further progress of human-like intelligent systems.

Novel four-hydrogen-bond assembled oligoamide dimer with pyrazoline moieties and its photoluminescent properties

In this paper, the synthesis and characterization of a triarylpyrazoline modified four-H-bonded molecular duplex are described. Its molecular structure has been confirmed by ^1H NMR and ESI-MS. The duplex emits strong pure blue light peaking at 448 and 452 nm under UV photoexcitation in solution and solid state, respectively, and its relative photoluminescence quantum efficiency in solution is determined as 0.778 using quinine sulfate as reference. In concentration of 〉40 mmol/L, the duplex can gelate DMSO, and the organogel formed shows good pure blue photoluminescence too. This novel duplex, for its well-defined structure and efficient photoluminescence property, is a prospective candidate for pure blue electroluminescent emitter.

Phase-Selective Gelators Based on p-Alkoxybenzoyl for Oil Spill Recovery and Dye Removal

Oil spills result in tremendous damage to the environment and ecosystem.In this study,several p-alkoxybenzoyl-based gelators(1,2a,2b,2c,3)synthesized from commercially available materials were designed for recovering oil from an oil–water mixture.Gels with remarkable gelation ability in various oils were characterized by nuclear magnetic resonance,Fourier transform infrared spectroscopy and X-ray diffraction to study the driving forces of self-assembly.Notably,these gelators could achieve the goal of recycling oil from the oil–water mixture at room temperature.In addition,gelator 2b could be used to remove toxic dyes from aqueous solutions with high efficiency.Therefore,these compounds were considered promising materials for oil spill recovery and dye removal due to their practicality and high efficiency.

Synthesis and Self-assembling of Coumarin-based Low-molecular Weight Organogelators

Four coumarin derivatives（4a-4d） with different alkoxy chains were synthesized. It was found that compound 4d showed a better gelation ability than the other compounds, for example, it could self-assemble into organogels in various organic fluids via ultrasound treatment or heating-cooling process, whereas compound 4c could only gel in a few mixed solvents and compounds 4a, 4b could not form organogel. The results from fluorescent and FT-IR spectra indicate that π-π interaction had an effect on the formation of the organogels of compound 4d besides H-bonding and van der Waals interaction, which were the driving forces for the self-assembling of compound 4c in gel state. The gel of compound 4d in toluene could emit strong fluorescence under UV irradiation and the [2＋2] cyclo-addition was suggested by ^1H NMR and fluorescence spectroscopy. This light-sensitive organogel might find application in optical materials.

Comparison of Chromatographic Performance for L-Phenylalanine-Derived Organic Phases on Silica by “Grafting from” and “Grafting to” Strategies

L-phenylalanine-derived polymerizable organogel, N’-octadecyl-Nα-(4-vinyl)-benzoyl-L-phenylalanineami- de (4) has been prepared according to the procedure described elsewhere. Compound 4 was successfully polymerized by surface initiated atom transfer radical polymerization (ATRP) from the initiator grafted silica particles (sil-poly4). It was also telomerized with 3-mercaptopropyltrimethoxysilane (MPS) and the telomer (T4) was grafted on to silica (sil-T4). TGA and elemental analysis measurement revealed that higher amount of polymer can graft by ATRP process than that of “grafting to” strategy. The results of 13C CP/MAS NMR measurement showed that the N-alkyl chain of the grafted polymers for both sil-poly4 and sil-T4 remained as less ordered gauche conformational form on silica surface and no inversion to trans form was occurred until temperature is increased up to 50?C. The retention of alkylbenzene samples showed that sil-poly4 prepared by “grafting from” method yielded extremely higher retention than conventional C18 phase however, sil-T4 prepared by conventional “grafting to” method showed lower retention than C18 phase. Aspects of molecular recognition were evaluated by the retention studies of a series of polycyclic aromatic hydrocarbons (PAHs) and aromatic positional isomers. We have observed sil-T4 yielded slightly higher selectivity for PAHs than sil-poly4 regardless the fact that it has low surface coverage and lower hydrophobic interactions. The enhanced selectivity observed for sil-T4 than C18 phases and sil-poly4 can be explained by the π - π interactions between the guest PAHs and carbonyl groups present in the polymer chain. In addition the aromatic moieties of compound 4 that aggregates through π - π interactions also contribute to the separation of PAHs for both sil-poly4 and sil-T4. The minimal π - π interactions between the carbonyl groups and guest molecules for sil-poly4 probably due to the presence of long chain initiator which restrict the polymer to form order thin layer over silica surface.

Fluoride-Responsive Organogel Based on Hydrazide Derivatives

An organogelator named N-[3-(hydroxy)-4-(dodecyloxy)-benzoyl]-N’ (4’-nitro-benzoyl) hydrazide (D12) was synthesized. It could form stable gels in some of the tested organic solvent. SEM images revealed that the molecules self- assembled into fibrous aggregates in the xerogels. The X-ray diffraction analysis showed that the xerogel exhibited a layered structure. FT-IR studies confirmed that intermolecular hydrogen bonding between C=O and N-H groups was the major driving force for gelation of organic solvents. The gel exhibited gel-sol transition and color change upon addition of F- . An extended conjugated system formed through the phenyl group and a five-membered ring based on intramolecular hydro-gen bonding between the oxygen atom near the deprotonation nitrogen atom and the other NH, which is responsible for the dramatic color change upon addition of F- .

Reconfigurable and orthogonal stiffness-structure patterning of dynamically crosslinked amphigels

Patterning diversified properties and surface structure of polymer materials are of great importance toward their potential in biology,optics,and electronics.However,achieving both the patternability of stiffness and microstructure in a reconfigurable manner remains challenging.Here,we prepare amphigels crosslinked by dynamic disulfide bonds,which can be reversibly swollen by immiscible water or liquid paraffin.In the paraffingel form,the materials exhibited a high modulus of 130 MPa due to densified hydrogen bonds.Whereas swollen by water,the modulus fell over two orders of magnitude owing to the destruction of the hydrogen bonds.Via regionalized swelling of the solvents,well-controlled and rewritable soft/stiff mechanical patterns can be created.On the other hand,the dynamic exchange of the disulfide crosslinking enables mechanophoto patterning to fabricate sophisticated macrogeometries and microstructures.The reconfigurable stiffness-structure patterning can be manipulated orthogonally,which will create more application opportunities beyond conventional hydrogels and organogels.

Scalable and Robust Bio-inspired Organogel Coating by Spraying Method Towards Dynamic Anti-scaling

Scaling usually causes serious problems in daily life and industrial production.Currently,developing passive anti-scaling coatings has shown promises to overcome this problem.In this work,we fabricated a scalable and robust bio-inspired organogel(BIO)coating,showing dynamic scale resistance in the oil/brine mixture.The oil layer of the BIO coating was utilized as a barrier to inhibit scale nucleation and reduce scale adhesion.The mechanical strength of the coating was optimized by regulating nanoparticle contents.Moreover,the universality of scale resistance was demonstrated by varying the types of nanoparticles,oils and scales.Compared with commercial pipeline materials,such as copper,this BIO coating significantly reduces scale deposition after 240-h scaling test(ca.93%reduction).Therefore,this study designs scalable and robust organogel coatings for sustainable scale resistance,which may be used for practical application in oil production.

Synthesis and ultraviolet/aggregation-induced emission investigation of novel tetraphenylvinyl hydrazone derivatives: efficient multimodal chemosensors for fluoride ion

Herein,three novel tetraphenylethylene hydrazone chemosensors TC12,SC16,and TC16 are prepared for the selective detection of F−.Two NH and one C=N units are incorporated into the sensors for better colorimetric responses,whereas the tetraphenyl unit is in charge of the aggregation-induced emission effect.Among them,compounds SC16 and TC16 form stable gels with some organic solvents.All the tetrahydrofuran/H2O solutions of the three compounds exhibit aggregation-induced emission effect,whereby the fluorescence emission increases by varying degrees with the volume of poor solvent water.Moreover,good aggregation-induced emission effects are observed in the self-assembly of SC16 and TC16.As a sample chemosensor,TC12 in tetrahydrofuran responds to F−selectively with high sensitivity,with the colorimetric and fluorometric detection limits of 8.25×10^(−7) mol·L^(-1) and 2.69×10^(−7) mol·L^(-1),respectively.The reversible gel-sol-gel phase transition and color changes indicate that both SC16-dimethyl sulfoxide and TC16-ethyl acetate gels specifically respond to F-with good sensitivity.The detection results are well supported by ultraviolet-visible spectroscopy,fluorescent spectroscopy,and 1H nuclear magnetic resonance.More importantly,the driving forces of gelation are visually clarified through the single crystal X-ray analysis of compound TOMe.

Wet‑Spinning Knittable Hygroscopic Organogel Fibers Toward Moisture‑Capture‑Enabled Multifunctional Devices

Atmospheric moisture exploitation is emerging as a promising alternative to relieve the shortage of freshwater and energy.Efforts to exploit hygroscopic materials featuring flexibility,programmability,and accessibility are crucial to portable and adaptable devices.However,current two-dimensional(2D)or three-dimensional(3D)-based hygroscopic materials are dif-ficult to adapt to diverse irregular surfaces and meet breathability,which severely hinders their wide applications in wearable and programmable devices.Herein,hygroscopic organogel fibers(HOGFs)were designed via a wet-spinning strategy.The achieved fibers were composed of the hydrophilic polymeric network,hygroscopic solvent,and photothermal/antibacterial Ag nanoparticles(AgNPs),enabling hygroscopic capacity,photothermal conversion,and antibacterial.Owing to the good knittable feature,the HOGFs can be readily woven to adjusted 2D textiles to function as an efficient self-sustained solar evaporator of 4-layer woven HOGF device with a saturated moisture capacity of 1.63 kg m^(-2) and water-releasing rate of 1.46 kg m^(-2) h^(-1).Furthermore,the 2D textile can be applied as a wearable dehumidification device to efficiently remove the evaporative moisture from human skin to maintain a comfortable environment.It can reduce the humidity from 90 to 33.4%within 12.5 min.In addition,the introduction of AgNPs can also endow the HOGFs with antibacterial features,demonstrat-ing significant potential in personal healthcare.

Preparation of optical active polydiacetylene through gelating and the control of supramolecular chirality

Achiral diacetylene 10,12-pentacosadinoic acid (PCDA) and a chiral low-molecular-weight organogelator could form co-gel in organic solvent and it could be polymerized in the presence of Zn(II) ion or in the corresponding xerogel under UV-irradiation. Optically active polydiacetylene (PDA) were subsequently obtained. Supramolecular chirality of PDA could be controlled by the chirality of gelators. Left-handed and right-handed helical fibers were obtained by using Land D-gelators in xerogels respectively, and CD spectra exhibited mirror-image circular dichroism. The PDA in xerogel exhibited typical blue-to-red transition responsive to the temperature and pH, while the supramolecular chirality of PDA showed a corresponding change.

Nanomagnetic Organogel Based on Dodecyl Methacrylate for Absorption and Removal of Organic Solvents

A novel nanomagnetic organogel was synthesized by in situ emulsion polymerization-crosslinking method using dodecyl methacrylate(DDMA) and styrene(St) as monomers, divinylbenzene(DVB) as a crosslinking agent, azobisisobutyronitrile(AIBN) as an initiator, and Fe_3O_4 as a nanomagnetic particle. Modification of the network was carried out by inclusion of the multi-walled carbon nanotubes(MWCNT) into the organogel matrix. The structure of the nanocomposite was characterized using FTIR spectroscopy, SEM,TEM, TGA/DTG, VSM, and BET analysis. The effects of various parameters such as the amount of crosslinker, initiator, Fe_3O_4, and reaction time as well as monomer ratio on the oil absorption of the organogel were studied. The synthesized organogel can absorb about35.5, 22.1, 29.86, 14.58, 17.6, 15.3, and 13.7 g·g^(-1) of CHCl_3, toluene, CH_2Cl_2, hexane, crude oil, gasoline, and diesel oil, under the optimized polymerization conditions, respectively. The nanocomposite organogels can be easily separated by a magnetic field after absorption of organic solvents.

Supramolecular self-assembly of two-component systems comprising aromatic amides/Schiff base and tartaric acid

The gelating properties and thermotropic behaviors of stoichiometric mixtures of aromatic amides 1,2,and the aromatic Schiffbase 3 with tartaric acid(TA)were investigated.Among the three gelators,2-TA exhibited superior gelating ability.Mixture 2-TA exhibits a smectic B phase and an unidentified smectic mesophase during both heating and cooling runs.The results of Fourier transform infrared spectroscopy and X-ray diffraction revealed the existence of hydrogen bonding and rc-ninteractions in 2-TA systems,which are likely to be the dominant driving forces for the supramolecular selfassembly.Additionally,it was established that all of the studied gel self-assemblies and mesophases possess alamellar structure.The anion response ability of the tetrahydrofuran gel of 2-TA was evaluated and it was found that it was responsive to the stimuli of F,Cl,Br,I,AcO.

A gelable pure organic luminogen with fluorescence-phosphorescence dual emission

Pure organic luminogens with room temperature phosphorescence(RTP) have drawn much attention due to their fundamental importance and promising applications in optoelectronic devices, bioimaging, sensing, etc. Fluorescence-phosphorescence dual emission at room temperature, however, is rarely observed in pure organic materials. Herein, we reported a metal-and heavy-atom free pure organic luminogen with tert-butyl groups, DtBuCZBP, which is ready to form organogels in dimethylsulfoxide(DMSO).It emits prompt and delayed fluorescence, as well as RTP, namely dual emission in as-prepared solid, gels and polymeric films.To the best of our knowledge, it is the first example of metal-and heavy-atom free pure organic gelator with RTP emission. Such unique RTP and moreover dual emission properties in different states make DtBuCZBP a potential material for diverse applications.

2,5-Dialkoxylphenyl-l,3,4-oxadiazoles as efficient organogelators and their self-assembling property

Four 2,5-dialkoxylphenyl-l,3,4-oxadiazoles are shown to be efficient organogelators. These com- pounds readily form stable gels in many organic solvents and their gelation property as well as supramolecular structures were investigated by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, 1H nuclear magnetic resonance （1H NMR）, and ultraviolet-visible spectroscopy （UV-vis）. The results indicate that the gelator molecules self-assemble into gels with elongated fibrous networks and layer structures, and van der Waals interaction is the main driving force.