New Peptide-Conjugated Chlorin-Type Photosensitizer Targeting Neuropilin-1 for Anti-Vascular Targeted Photodynamic Therapy

Photodynamic therapy (PDT) is a cancer treatment modality that requires three components, namely light, dioxygen and a photosensitizing agent. After light excitation, the photosensitizer (PS) in its excited state transfers its energy to oxygen, which leads to photooxidation reactions. In order to improve the selectivity of the treatment, research has focused on the design of PS covalently attached to a tumor-targeting moiety. In this paper, we describe the synthesis and the physico-chemical and photophysical properties of six new peptide-conjugated photosensitizers designed for targeting the neuropilin-1 (NRP-1) receptor. We chose a TPC (5-(4-carboxyphenyl)-10,15, 20-triphenyl chlorine as photosensitizer, coupled via three different spacers (aminohexanoic acid, 1-amino-3,6-dioxaoctanoic acid, and 1-amino-9-aza-3,6,12,15-tetraoxa-10-on-heptadecanoic acid) to two different peptides (DKPPR and TKPRR). The affinity towards the NRP-1 receptor of the conjugated chlorins was evaluated along with in vitro and in vivo stability levels. The tissue concentration of the TPC-conjugates in animal model shows good distribution, especially for the DKPPR conjugates. The novel peptide–PS conjugates proposed in this study were proven to have potential to be further developed as future NRP-1 targeting photodynamic therapy agent.     

Mechanical Properties of Dry-Pressed Ceramic Green Products: The Effect of the Binder

The strength of alumina green samples prepared by uniaxial pressing of powders spray-dried with two binders such as poly(ethylene glycol) or poly(vinyl alcohol) is discussed in terms of (i) the adhesive properties of the polymer-rich external layer of spray-dried granules and (ii) the mechanical properties of this layer. A transition from intra- to intergranular fracture is observed when the glass transition temperature of the binder increases. The influence of the binder on the defect size distribution in the green products is investigated using the classical Weibull statistics.     

On the Strategic Impact of the Degenerative Transfer of Xanthates on Synthetic Planning

The present brief account relates synthetic endeavours revolving around a novel chemistry of xanthates (dithiocarbonates) being developed in our group. The degenerative reversible transfer of xanthates has a unique ability to store reactive radicals in a dormant form, and thereby to enhance their lifetime in a concentrated medium, while at the same time, regulating their absolute and relative concentrations. It allows intermolecular radical additions even to unactivated alkenes, and can promote otherwise sluggish radical processes, such as 5-endo, 6-exo, 6-endo, 7-endo, and 8-endo cyclisations, as well as ring closures on (hetero)aromatic structures. This chemistry has proved remarkably versatile and powerful, both for solving synthetic problems and for the industrial production of block copolymers through the RAFT/MADIX technology.     

Synthesis,photophysical properties,and application of optical brighteners based on stilbene-oxadiazole derivatives

A series of symmetrical optical brighteners based on stilbene-oxadiazole derivatives were prepared by the simple synthetic route of a condensation reaction between 4,4′-dicarboxystilbene and N,N′-carbonyldiimidazole reagent, forming stilbene 4,4′-ethene-1,2-diyldibenzohydrazide as a key intermediate. The obtained compounds were characterised by analysis of nuclear magnetic resonance, mass spectrometry, and elemental analysis data. The absorption maximum wavelength, fluorescence emission wavelength, and fluorescence quantum yield were measured in N,N-dimethylformamide solution at room temperature, and the fluorescence properties of the prepared compounds in the solid state were observed and measured. The compounds exhibited bluish and greenish fluorescence emission, with the fluorescence quantum yield in the range 0.2–0.8; the effects of substituents on the emission spectra of these compounds were interpreted. The prepared compounds were applied as optical brighteners to polyester and polyamide-6 fabrics at various concentrations, and their CIE whiteness index and fastness properties were studied.     

Experimental,equilibrium modelling,and column design for the reactive separation of biomass-derived 2-furoic acid

Electrochemical conversion of biomass to value-added chemicals has gained impetus in recent years. Herein, we present a methodology for recovering biomass-derived 2-furoic acid from the dilute aqueous stream by reactive extraction. The reactive extraction was performed using a chemical extractant, trioctylamine (TOA), with diluents (octanol, chloroform, and diethyl ether). Equilibrium parameters influencing the recovery of 2-furoic acid were evaluated. Using TOA in various diluents, the 2-furoic acid was recovered with 85%–99% efficiency. A 1:1 complex of the 2-furoic acid—TOA was formed in the organic phase, and the experimental equilibrium complexation constant was compared with that obtained from the relative basicity and Langmuir models. The equilibrium parameters were used for column design to estimate the solvent to feed ratio (S/F) and the number of theoretical stages (NTS). The NTS required is 12 to attain 99% recovery of 2-furoic acid in counter-current extraction. The present study sheds light on the reactive extraction process adopted for process intensification with electrochemical conversion, paving the way for the commercialization of valuable products obtained from biomass.     

A review of the desert gold jojoba (Simmondsia chinensis) whole plant,oil, and meal: Phytochemical composition,medicinal uses,and detoxification

Simmondsia chinensis (Link) C.K. Schneider (Jojoba) is a valuable shrub that can bear harsh conditions and is cultivated in many countries globally. Its prominence originates from the unique oil that constitutes more than 50% of the seeds. The great economic value of jojoba oil is highlighted in many fields, especially the cosmetic industry. The remaining meal, which is rich in proteins, constitutes a good source for cattle feeding. However, the presence of antinutritional principles in the meal limited its use and encouraged the researchers to find different ways for its detoxification. The detoxification ways of jojoba meal included physical, biological, and chemical treatments. The phytochemical composition of the oil was deeply studied, but for the remaining plant, only few studies have reported its chemical composition. Jojoba oil composed of wax esters (97%), fatty acids, fatty alcohols, sterols, and small percentage of vitamin E. Jojoba possesses a long traditional history. It has been used in folklore for treatment of cold, dysuria, and obesity. Many recent studies reported its medicinal and pharmacological properties like antioxidant, anti-inflammatory, antimicrobial, anticancer, anti-acne, anti-psoriasis, wound healing, and hepatoprotective activities. Many of these biological activities have been attributed to the presence of several phytochemicals such as simmondsin and phenolic compounds. In this review, the authors will highlight the previous phytochemical studies, medicinal applications of jojoba oil and different plant parts, and the various ways of meal detoxification.     

Coupling hydrothermal liquefaction and aqueous phase reforming for integrated production of biocrude and renewable H2

Lignin-rich stream from lignocellulosic ethanol production was converted into biocrude by continuous hydrothermal liquefaction (HTL) while hydrogen was produced by aqueous phase reforming (APR) of the HTL aqueous by-product. The effects of Na₂CO₃ and NaOH were investigated both in terms of processability of the feedstock as well as yield and composition of the obtained products. A maximum biocrude yield of 27 wt% was reached in the NaOH-catalyzed runs. A relevant amount of dissolved phenolics were detected in the co-produced aqueous phase (AP), and removed by liquid–liquid extraction using butyl acetate or diethyl ether, preserving the APR catalyst stability and reaching an hydrogen yield up to 146 mmol H₂ L⁻¹ AP. Preliminary mass balances integrating HTL and APR showed that the hydrogen provided by APR may account for up to 46% of the hydrogen amount theoretically required for upgrading the HTL biocrude, thus significantly improving the process performance and sustainability.     

The pseudo-single-phase,base-catalyzed transmethylation of soybean oil

The base-catalyzed transmethylation of soybean oil has been studied under conditions whereby the reaction starts as a single phase, but later becomes two phases as glycerol separates. Methanol/oil molar ratios of 6∶1 were used at 23°C. The catalysts were sodium hydroxide (0.5, 1.0, and 2.0 wt%), potassium hydroxide (1.0 and 1.4 wt%), and sodium methoxide (0.5, 1.0, and 1.35 wt%), all concentrations being with respect to the oil. Oxolane (tetrahydrofuran) was used to form a single reaction phase. The reactions deviated from homogeneous kinetics as glycerol separated, taking with it most of the catalyst. When 1.0 wt% sodium hydroxide was used, the methyl ester content reached 97.5 wt% after 4 h, compared with 85–90 wt% in the two-phase reaction. Sodium hydroxide (1.0 wt%), sodium methoxide (1.35 wt%), and potassium hydroxide (1.4 wt%) gave similar results, presumably because the same number of moles was used. The ASTM biodiesel specification for chemically bound glycerol was achieved after only 3 min when 2.0 wt% sodium hydroxide was used. However, the standard was not achieved after 4 h when 1.0 wt% sodium hydroxide was used, the MG content being 1.1–1.6 wt%. The use of 2.0 wt% catalyst is commercially impractical.     

Utilization of cellulose‐triacetate‐blended membranes for carrier‐mediated transport of some metal ions

In this study, cellulose triacetate was used as a suitable base polymer for polymer‐blended membranes for ion sensing and separation. Polymer‐blended membranes were prepared with the solvent casting technique in the presence of mixed plasticizer and a metal ion carrier known as an ionophore. 7‐Dodecenyl‐8‐hydroxy‐quinoline and N,N′‐diphenylethyl Kemp's triacid diamide, in addition to the newly synthesized 8‐[N‐acetyl‐O‐(4‐tert‐butyl benzyl)‐L‐tyrosylamino] quinoline, were used as representative examples for ionophores. The membranes were evaluated through the transport of copper and lead ions into 0.1M nitric acid as the receiving phase. The concentrations of the investigated metal ions in both phases were assayed by atomic absorption spectrometry. From this study, it can be concluded that the efficiency of the membrane, either as an ion‐transporting or as an ion‐extracting condidate, is controlled by the amount of the immobilized ionophore, the immobilization time within the membrane matrix while in contact with the receiving phase, the nature of the ionophore–metal ion complex, and so on. The carrier‐mediated transport mechanism was also investigated. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2008–2015, 2001     

Effects of processing on oxidative stability of sesame oil extracted from intact and dehulled seeds

Oxidative stability of oils extracted from intact and dehulled sesame seeds was determined by monitoring changes in fatty acid composition, iodine value (IV), peroxide value (PV), conjugated diene (CD), para-anisidine value (p-AV), and 2-thiobarbituric acid (TBA) value and by nuclear magnetic resonance spectroscopy after storage under Schaal oven conditions at 65°C for up to 35 d. The oils from coated seeds were more stable, as reflected in PV, CD, p-AV and TBA values, than those extracted from dehulled seeds after roasting at 200°C, steaming at 100°C, roasting at 200°C plus steaming, or microwaving at 2450 MHz, except for TBA values of oil from microwaved seeds. After 35 d of storage at 65°C, the CD, p-AV, and TBA values of extracted oil from dehulled microwaved seeds were 17.72, 10.20, and 1.22, respectively, while those of their coated counterparts were significantly (P<0.05) different at 14.20, 16.47, and 1.26, respectively. Few significant changes were evident in the fatty acid composition of oil obtained from either coated and dehulled seeds subjected to different treatments. Nuclear magnetic resonance analyses found that R_ao (aliphatic to olefinic protons) and R_ad (aliphatic to diallylmethylene protons) ratios increased steadily over the entire storage period, which indicated progressive oxidation of unsaturated fatty acids.