Synthesis and Properties of Nitrogen-Doped Carbon Quantum Dots Using Lactic Acid as Carbon Source.

Nitrogen-doped carbon quantum dots (N-CQDs) were synthesized in a one-step hydrothermal technique utilizing L-lactic acid as that of the source of carbon and ethylenediamine as that of the source of nitrogen, and were characterized using dynamic light scattering, X-ray photoelectron spectroscopy ultraviolet-visible spectrum, Fourier-transformed infrared spectrum, high-resolution transmission electron microscopy, and fluorescence spectrum. The generated N-CQDs have a spherical structure and overall diameters ranging from 1-4 nm, and their surface comprises specific functional groups such as amino, carboxyl, and hydroxyl, resulting in greater water solubility and fluorescence. The quantum yield of N-CQDs (being 46%) is significantly higher than that of the CQDs synthesized from other biomass in literatures. Its fluorescence intensity is dependent on the excitation wavelength, and N-CQDs release blue light at 365 nm under ultraviolet light. The pH values may impact the protonation of N-CQDs surface functional groups and lead to significant fluorescence quenching of N-CQDs. Therefore, the fluorescence intensity of N-CQDs is the highest at pH 7.0, but it decreases with pH as pH values being either more than or less than pH 7.0. The N-CQDs exhibit high sensitivity to Fe3+ ions, for Fe3+ ions would decrease the fluorescence intensity of N-CQDs by 99.6%, and the influence of Fe3+ ions on N-CQDs fluorescence quenching is slightly affected by other metal ions. Moreover, the fluorescence quenching efficiency of Fe3+ ions displays an obvious linear relationship to Fe3+ concentrations in a wide range of concentrations (up to 200 µM) and with a detection limit of 1.89 µM. Therefore, the generated N-CQDs may be utilized as a robust fluorescence sensor for detecting pH and Fe3+ ions.

Surface Modification of Poly(l-lactic acid) through Stereocomplexation with Enantiomeric Poly(d-lactic acid) and Its Copolymer.

Poly(l-lactic acid) with high molecular weight was used to prepare PLLA films by means of the solvent casting technique. Poly(d-lactic acid) (PDLA) and poly(d-lactic acid-co-glucose) copolymer (PDLAG) with a low molecular weight were synthesized from d-lactic acid and glucose through melt polycondensation. PLLA films were immersed in PDLA or PDLAG solution to prepare surface-modified PLLA films. The modified PLLA film presented stereocomplex crystal (SC) on its surface and homogeneous crystals (HC) in its bulk. The HC structure and surface morphology of modified PLLA films were obviously damaged by PDLA or PDLAG solution. With increasing immersion time, the PLLA films modified by PDLA decreased both the HC and SC structure, while the PLLA films modified by PDLAG increased the SC structure and decreased the HC structure. Hydrophilic glucose residues of PDLAG on the surface would improve the hydrophilicity of surface-modified PLLA films. Moreover, the hydrophilicity of glucose residues and the interaction of glucose residues with lactic acid units could retard HC destruction and SC crystallization, so that PLLA films modified by PDLAG possessed lower melting temperatures of HC and SC, the crystallinity of SC and the water contact angle, compared with PDLAG-modified PLLA films. The SC structure could improve the heat resistance of modified PLLA film, but glucose residues could block crystallization to promote the thermal degradation of PLA materials. The surface modification of PLLA films will improve the thermal stability, hydrophilicity and crystallization properties of PLA materials, which is essential in order to obtain PLA-based biomaterials.

Preparation and Properties of Stereocomplex of Poly(lactic acid) and Its Amphiphilic Copolymers Containing Glucose Groups.

The stereocomplex of poly(lactic acid) containing glucose groups (sc-PLAG) was prepared by solution blending from equal amounts of poly(l-lactic acid) (PLLA) and poly(d-lactic acid-co-glucose) (PDLAG), which were synthesized from l- and d-lactic acid and glucose by melt polycondensation. The methods, including 1H nuclear magnetic resonance spectroscopy (1H NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), X-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), polarizing microscope (POM), scanning electron microscope (SEM), transmission electron microscope (TEM), and contact angle were used to determine the effects of the stereocomplexation of enantiomeric poly(lactic acid) (PLA) units, the amphiphilicity due to glucose residues and lactic acid units, and the interaction of glucose residues with lactic units on the crystallization performance, hydrophilicity, thermal stability, and morphology of samples. The results showed PDLAG was multi-armed, and partial OH groups of glucose residues in PDLAG might remain unreacted. The molecular weight (Mw), dispersity (Ɖ), and glucose proportion in the chain of PDLAG thereby had significant effects on sc-PLAG. There were the stereocomplexation of enantiomeric lactic units and the amphiphilic self-assembly of PDLAG in sc-PLAG, which resulted in glucose groups mainly in the surface phase and lactic units in the bulk phase. The sc-PLAG only possessed the stereocomplex crystal owing to the interaction between nearly equimolar of l-lactic units of PLLA and d-lactic units of PDLAG, and had no homo-crystallites of l- or d-lactic units, which improved the melting temperature (Tm) of sc-PLAG about 50 °C higher than that of PLLA. Glucose groups in sc-PLAG played an important role by forming heterogeneous nucleation, promoting amphiphilic self-assembly, and affecting the ordered arrangement of lactic units. The glass transition temperature (Tg), the melting temperature (Tm), crystallinity, crystallization rate, and water absorption of sc-PLAG showed similar changes with the increased glucose content in feeding. All these parameters increased at first, and the maximum appeared as glucose content in feeding about 2%, such as the maximum crystallinity of 48.8% and the maximum water absorption ratio being 11.7%. When glucose content in feeding continued increasing, all these performances showed a downward trend due to the decrease of arrangement regularity of lactic acid chains caused by glucose groups. Moreover, the contact angle of sc-PLAG decreased gradually with the increased glucose content in feeding to obtain the minimum 77.5° as the glucose content in feeding being 5%, while that of PLLA was 85.0°. The sc-PLAG possessed a regular microsphere structure, and its microspheres with a diameter of about 200 nm could be observed. In conclusion, sc-PLAG containing proper glucose amount could effectively enhance the crystallinity, hydrophilicity, and thermal stability of PLA material, which is useful for drug delivery, a scaffold for tissue engineering, and other applications of biomedicine.