ABSTRACT
We correct a mistake in [Opt. Express27, 11914 (2019)10.1364/OE.27.011914] when calculating the focal length of the Kerr lens with the measured values of the nonlinear refractive index n2 and parameters of a prototypical self-mode-locking VECSEL cavity. We therefore update Fig. 1 of the original publication. The new calculation yields a significantly larger value of the Kerr lens focal length leading to a smaller perturbation of the cavity beam profile.
ABSTRACT
Self-mode-locking has become an emerging path to the generation of ultrashort pulses with vertical-external-cavity surface-emitting lasers. In our work, a strong Kerr nonlinearity that is so far assumed to give rise to mode-locked operation is evidenced and a strong nonlinearity enhancement by the microcavity is revealed. We present wavelength-dependent measurements of the nonlinear absorption and nonlinear refractive index change in a gain chip using the Z-scan technique. We report negative nonlinear refraction up to 5x10-12 cm2/W in magnitude in the (InGa)As/Ga(AsP) material system close to the laser design wavelength, which can lead to Kerr lensing. We show that by changing the angle of incidence of the probe beam with respect to the gain chip, the Kerr nonlinearity can be wavelength-tuned, shifting with the microcavity resonance. Such findings may ultimately lead to novel concepts with regard to tailored self-mode-locking behavior achievable by peculiar Kerr-lens chip designs for cost-effective, robust and compact fs-pulsed semiconductor lasers.
ABSTRACT
Carrier-free nanomedicines offer advantages of extremely high drug loading capacity (>80%), minimal non-drug constituent burden, and facile preparation processes. Numerous studies have proved that multimodal cancer therapy can enhance chemotherapy efficiency and mitigate multi-drug resistance (MDR) through synergistic therapeutic effects. Upon penetration into the tumor matrix, nanoparticles (NPs) are anticipated to be uptaken by cancer cells, primarily through clathrin-meditated endocytosis pathways, leading to their accumulation in endosomes/lysosomes within cells. However, endo/lysosomes exhibit a highly degradative environment for organic NPs and drug molecules, often resulting in treatment failure. Hence, this study designed a lysosomal escape mechanism with carrier-free nanomedicine, combining the chemotherapeutic drug, curcumin (Cur), and the photothermal/photodynamic therapeutic drug, indocyanine green (ICG), for synergistic cancer treatment (ICG-Cur NPs) via a facile preparation process. To facilitate endo/lysosomal escape, ICG-Cur NPs were modified with metal-phenolic networks (MPNs) of different thickness. The results indicate that a thick MPN coating promotes rapid endo/lysosomal escape of ICG-Cur NPs within 4 h and enhances the photothermal conversion efficiency of ICG-Cur NPs by 55.8%, significantly improving anticancer efficacy in both chemo- and photo-therapies within 3D solid tumor models. This finding underscores the critical role of endo/lysosomal escape capacity in carrier-free drug NPs for therapeutic outcomes and offers a facile solution to achieve it.
Subject(s)
Antineoplastic Agents , Curcumin , Indocyanine Green , Lysosomes , Lysosomes/metabolism , Lysosomes/drug effects , Humans , Indocyanine Green/chemistry , Indocyanine Green/pharmacology , Antineoplastic Agents/chemistry , Antineoplastic Agents/pharmacology , Animals , Curcumin/chemistry , Curcumin/pharmacology , Mice , Nanoparticles/chemistry , Nanomedicine , Photosensitizing Agents/chemistry , Photosensitizing Agents/pharmacology , Drug Screening Assays, Antitumor , Endosomes/metabolism , Photochemotherapy , Cell Survival/drug effects , Particle Size , Cell Proliferation/drug effects , Mice, Inbred BALB C , Cell Line, Tumor , Female , Neoplasms/drug therapyABSTRACT
Four new ternary crystalline molecular complexes have been synthesised from a common 3,5-dinitrobenzoic acid (3,5-dnda) and 4,4'-bipyridine (bipy) pairing with a series of amino-substituted aromatic compounds (4-aminobenzoic acid (4-aba), 4-(N,N-dimethylamino)benzoic acid (4-dmaba), 4-aminosalicylic acid (4-asa) and sulfanilamide (saa)). The ternary crystals were created through the application of complementary charge transfer and hydrogen-bonding interactions. For these systems a dimer was created through a charge-transfer interaction between two of the components, while hydrogen bonding between the third molecule and this dimer completed the construction of the ternary co-crystal. All resulting structures display the same acidâ â â pyridine interaction between 3,5-dnba and bipy. However, changing the third component causes the proton of this bond to shift from neutral OHâ â â N to a salt form, O(-) â â â HN(+) , as the nature of the group hydrogen bonding to the carboxylic acid was changed. This highlights the role of the crystal environment on the level of proton transfer and the utility of ternary systems for the study of this process.
Subject(s)
Nitrobenzoates/chemistry , Pyridines/chemistry , Crystallography, X-Ray , Dimerization , Hydrogen Bonding , Molecular Conformation , Quantum Theory , ThermodynamicsABSTRACT
Raman spectroscopy has proven to be a very effective approach for the detection of microorganisms colonising hostile environments on Earth. The ExoMars rover, due for launch in 2018, will carry a Raman laser spectrometer to analyse samples of the martian subsurface collected by the probe's 2-m drill in a search for similar biosignatures. The martian surface is unprotected from the flux of cosmic rays, an ionising radiation field that will degrade organic molecules and so diminish and distort the detectable Raman signature of potential martian microbial life. This study employs Raman spectroscopy to analyse samples of two model organisms, the cyanobacterium Synechocystis sp. PCC 6803 and the extremely radiation resistant polyextremophile Deinococcus radiodurans, that have been exposed to increasing doses of ionising radiation. The three most prominent peaks in the Raman spectra are from cellular carotenoids: deinoxanthin in D. radiodurans and ß-carotene in Synechocystis. The degradative effect of ionising radiation is clearly seen, with significant diminishment of carotenoid spectral peak heights after 15 kGy and complete erasure of Raman biosignatures by 150 kGy of ionising radiation. The Raman signal of carotenoid in D. radiodurans diminishes more rapidly than that of Synechocystis, believed to be due to deinoxanthin acting as a superior scavenger of radiolytically produced reactive oxygen species, and so being destroyed more quickly than the less efficient antioxidant ß-carotene. This study highlights the necessity for further experimental work on the manner and rate of degradation of Raman biosignatures by ionising radiation, as this is of prime importance for the successful detection of microbial life in the martian near subsurface.
Subject(s)
Life , Radiation, Ionizing , Spectrum Analysis, Raman/methods , Deinococcus/isolation & purification , Mars , Synechocystis/isolation & purificationABSTRACT
The efficiency of reduced volume PCR amplification was studied using the VeriFiler™ Express PCR Amplification Kit. Full (25 µL) and reduced (5 µL) volumes were tested in parallel to identify any differences in template DNA sensitivity and other electropherogram parameters. Both volumes produced full DNA profiles down to 0.08 ng/µL DNA concentration at 26 PCR cycles; however, reduced volume produced higher peak heights due to increased signal intensities. Significant difference (p-value ≤ 0.05) in heterozygote peak height ratios was observed between both volumes, where the reduced volume threshold was lowered to 0.6 to accommodate all data points. However, no significant difference (p-value > 0.05) was identified in the stutter ratios between both volumes. The analytical threshold for reduced volume was also determined to be 150 RFU with the presence of template DNA in PCR amplification. When the optimized reduced volume parameters were tested on DNA extracted from buccal swab samples using Prep-n-Go™ Buffer, good quality DNA profiles were produced. Overall, the reduced volume not only showed better results compared to the full volume, but also enable more samples to be processed with a PCR amplification kit, thus reduced the cost.
Subject(s)
DNA Fingerprinting , Microsatellite Repeats , DNA/genetics , DNA Fingerprinting/methods , Heterozygote , Polymerase Chain Reaction/methodsABSTRACT
Overcoming the slow oxygen reduction reaction (ORR) kinetics at the cathode of the hydrogen fuel cells requires the use of electrocatalysts containing expensive and scare platinum to achieve reasonable performance, hampering widespread use of the technology due to high material costs and sustainability issues. One option available to tackle this issue is to use new designs to create nanomaterials which achieve excellent electrocatalytic performances and long-lasting stabilities whilst using less platinum than is currently required. Reliably producing nanomaterials with predictable activities and stabilities using simple, safe, and scalable methods is an important research topic to the advancement of fuel cell technologies. The oxygen reduction reaction occurs at the surface of electrocatalytic materials, and since nanomaterial structures exhibit different catalytic activities, their shapes have a strong relationship to the final performance. Seed-mediated synthesis can be used to control the shape of materials with the aim of obtaining products with the most desirable surface properties for the ORR. This review summarized the current advancement of the synthesis of platinum-based ORR and provided the insights for the future development of this field.
ABSTRACT
With an exponential rise in antimicrobial resistance and stagnant antibiotic development pipeline, there is, more than ever, a crucial need to optimize current infection therapy approaches. One of the most important stages in this process requires rapid and effective identification of pathogenic bacteria responsible for diseases. Current gold standard techniques of bacterial detection include culture methods, polymerase chain reactions, and immunoassays. However, their use is fraught with downsides with high turnaround time and low accuracy being the most prominent. This imposes great limitations on their eventual application as point-of-care devices. Over time, innovative detection techniques have been proposed and developed to curb these drawbacks. In this review, a systematic summary of a range of biosensing platforms is provided with a strong focus on technologies conferring high detection sensitivity and specificity. A thorough analysis is performed and the benefits and drawbacks of each type of biosensor are highlighted, the factors influencing their potential as point-of-care devices are discussed, and the authors' insights for their translation from proof-of-concept systems into commercial medical devices are provided.
Subject(s)
Biosensing Techniques , Point-of-Care Systems , Anti-Bacterial Agents/pharmacology , Anti-Bacterial Agents/therapeutic use , Bacteria , Biosensing Techniques/methods , ImmunoassayABSTRACT
The likelihood of finding intact cellular structures on the surface or in the near subsurface of the martian regolith is slim, due in part to the intense bombardment of the surface by ionizing radiation from outer space. Given that this radiation is predicted to be so intense that it would render a living cell inactive within minutes, it is logical to search for evidence of microbial life by looking for molecules produced by the breakdown of cellular matter. This "pool" of molecules, known as biomarkers, consists of a range of species with various functionalities that make them likely to interact with minerals in the martian regolith. Raman spectroscopy, a molecularly specific analysis method utilized for detecting organic biomarkers among inorganic geomaterials, suffers from low signal intensity when the concentration of organics is as low as it appears to be on the martian surface. This article describes the utility of a surface-enhanced Raman spectroscopy (SERS) method used to detect extremely low levels of biomarkers that were passively adhered to mineral surfaces in a method that represents how this interaction would take place in a natural environment on Mars. The methodology showed promise for the detection of multiple classes of biomarkers.
Subject(s)
Extraterrestrial Environment , Mars , Environment , Minerals , Spectrum Analysis, RamanABSTRACT
Antibiotics have played an important role in the treatment of bacteria related infections. However, the rapid emergence of multidrug-resistant bacteria and limited number of antibiotics available is a great challenge to humankind. To address this problem, we are proposing a photosensitizer-modified biodegradable zeolitic imidazolate framework-8 nanocomposite that can kill not only Gram-positive bacteria Staphylococcus aureus, but also methicillin-resistant Staphylococcus aureus (MRSA) with high efficacy. In vivo testing revealed that these nanocomposites are highly effective for in vivo wound disinfection with minimal side-effects. In conclusion, this photosensitizer-modified biodegradable nanocomposite could be very promising for a synergistic antibacterial therapy to overcome MRSA.
Subject(s)
Anti-Bacterial Agents/pharmacology , Methicillin-Resistant Staphylococcus aureus/drug effects , Nanocomposites/chemistry , Photosensitizing Agents/pharmacology , Porphyrins/pharmacology , Zeolites/pharmacology , Anti-Bacterial Agents/chemistry , Chlorophyllides , Humans , Microbial Sensitivity Tests , Particle Size , Photosensitizing Agents/chemistry , Porphyrins/chemistry , Surface Properties , Zeolites/chemistryABSTRACT
Terahertz frequency time-domain spectroscopy has been used to analyse a wide range of samples containing cocaine hydrochloride, heroin and ecstasy--common drugs-of-abuse. We investigated real-world samples seized by law enforcement agencies, together with pure drugs-of-abuse, and pure drugs-of-abuse systematically adulterated in the laboratory to emulate real-world samples. In order to investigate the feasibility of automatic spectral recognition of such illicit materials by terahertz spectroscopy, principal component analysis was employed to cluster spectra of similar compounds.
Subject(s)
Cocaine/analysis , Heroin/analysis , Substance Abuse Detection/methods , Terahertz Spectroscopy/methods , Principal Component Analysis , Terahertz ImagingABSTRACT
Multidrug resistant bacterial infection remains a significant public concern. In this report, photosensitizer Chlorin e6 doped silica was synthesized. This hybrid structure exhibits enhanced photostability and high antibacterial efficiency towards Staphylococcus aureus (S. aureus) and methicillin-resistant S. aureus (MRSA). In summary, this work demonstrates an effective platform to improve the efficiency of antibiotics for better treatment of wound infections.
Subject(s)
Anti-Bacterial Agents/pharmacology , Methicillin-Resistant Staphylococcus aureus/drug effects , Nanoparticles/chemistry , Porphyrins/chemistry , Silicon Dioxide/chemistry , Anti-Bacterial Agents/chemical synthesis , Anti-Bacterial Agents/chemistry , Chlorophyllides , Drug Stability , Light , Radiation-Sensitizing Agents/chemistry , Singlet Oxygen/chemistry , Singlet Oxygen/metabolism , Staphylococcus aureus/drug effectsABSTRACT
Over 500 victims of the Spanish Civil War (1936-1939) were buried in the cemetery of La Carcavilla (Palencia, Spain). White material, observed in several burials, was analyzed with Raman spectroscopy and powder XRD, and confirmed to be lime. Archaeological findings at La Carcavilla's cemetery show that the application of lime was used in an organized way, mostly associated with coffinless interments of victims of Francoist repression. In burials with a lime cast, observations made it possible to draw conclusions regarding the presence of soft tissue at the moment of deposition, the sequence of events, and the presence of clothing and other evidence. This study illustrates the importance of analyzing a burial within the depositional environment and taphonomic context.
Subject(s)
Burial , Calcium Compounds , Oxides , Cemeteries , Forensic Anthropology , History, 20th Century , Humans , Spain , Spectrum Analysis, Raman , WarfareABSTRACT
The design of a melt synthesis of the first air-stable formulation of the metastable form III of paracetamol is derived from thermo-spectroscopic and thermo-diffraction experiments. Melt crystallisation in the presence of ß-1,4-saccharides produces form III selectively and the excipients appear to act as stabilising 'active' templates of the metastable polymorph.
ABSTRACT
Calcium and magnesium carbonates are important minerals found in sedimentary environments. Although sandstones are the most common rock colonized by endolith organisms, the production of calcium and magnesium carbonates is important in survival strategies of organisms and as a source for the removal of oxalate ions. Extremophile organisms in some situations may convert or destroy carbonates of calcium and magnesium, which gives important information about the conditions under which these organisms can survive. The identification on the surface of Mars of 'White Rock' formations, in Juventae Chasma or Sabaea Terra, as possibly carbonate rocks makes the study of these minerals a prerequisite of remote Martian exploration. Here, we show the protocol for the identification by Raman spectroscopy of different calcium and magnesium carbonates and we present a database of relevance in the search for life, extinct or extant, on Mars; this will be useful for the assessment of data obtained from remote, miniaturized Raman spectrometers now proposed for Mars exploration.
Subject(s)
Calcium Carbonate/chemistry , Magnesium/chemistry , Spectrum Analysis, Raman , Mars , Spectrum Analysis, Raman/methodsABSTRACT
The creation of ternary multi-component crystals through the introduction of 18-crown-6 to direct the hydrogen-bonding motifs of the other molecular components was investigated for 3,5-dinitrobenzoic acid (3,5-dnba) with 4-aminobenzoic acid (4-aba). The creation of a binary complex between 18-crown-6 and 4-aba (C12H24O6·2C7H7NO2)2 and a ternary salt between 3,5-dnba, 18-crown-6 and 4-aba (C12H24O6·C7H8NO2(+)·C7H3N2O6(-)·C7H4N2O6) were confirmed by single-crystal structure determination. In both structures, the amino molecules bind to the crown ether through N-H...O hydrogen bonds, leaving available only a single O atom site on the crown with restricted geometry to potentially accept a hydrogen bond from 3,5-dnba. While 3,5-dnba and 4-aba form a binary co-crystal containing neutral molecules, the shape-selective nature of 18-crown-6 preferentially binds protonated amino molecules, thereby leading to the formation of the ternary salt, despite the predicted low concentration of the protonated species in the crystallizing solution. Thus, through the choice of crown ether it may be possible to control both location and nature of the available bonding sites for the designed creation of ternary crystals.
ABSTRACT
Gamma-hydroxybutyric acid (GHB) is a drug-of-abuse that has recently become associated with drug-facilitated sexual assault, known as date rape. For this reason the drug is commonly found 'spiked' in alcoholic beverages. When GHB is in solution it may undergo conversion into the corresponding lactone, Gamma-butyrolactone (GBL). Studies have been carried out to determine the detection limits of GHB and GBL in various solutions by Raman spectroscopy and to monitor the interconversion of GHB and GBL in solution with different pH conditions and temperature. In this study, a portable Raman spectrometer was used to study the interconversion of GHB and GBL in water and ethanol solutions as a function of pH, time, and temperature. The aim of this was to determine the optimum pH range for conversion in order to relate this to the pH ranges that the drug is likely to be subjected to, first in spiked beverages and secondly after ingestion in the digestive system. The aim was also to identify a timescale for this conversion in relation to possible scenarios, for example if GHB takes a number of hours to convert to GBL, it is likely for the beverage to be ingested before esterification can take place. GHB and GBL were then spiked into a selection of beverages of known pH in order to study the stability of GHB and GBL in real systems.
Subject(s)
4-Butyrolactone/analysis , Alcoholic Beverages/analysis , Carbonated Beverages/analysis , Hydroxybutyrates/analysis , Illicit Drugs/analysis , Spectrum Analysis, Raman/methods , Humans , Hydrogen-Ion Concentration , Rape , Substance Abuse Detection/methodsABSTRACT
Gamma hydroxybutyric acid (GHB), also known as 'liquid ecstasy', has recently become associated with drug-facilitated sexual assaults, known colloquially as 'date rape', due to the ability of the drug to cause loss of consciousness. The drug is commonly found 'spiked' into alcoholic beverages, as alcohol increases its sedative effects. Gamma hydroxybutyric acid and the corresponding lactone gamma-butyrolactone (GBL) will reach an equilibrium in solution which favours the lactone in basic conditions and GHB in acidic conditions (less than pH 4). Therefore, we have studied both GHB and GBL, as a mildly acidic beverage 'spiked' with GHB will contain both GHB and GBL. We report the analysis of GHB as a sodium salt and GBL, its precursor, using bench-top and portable Raman spectroscopy. It has been demonstrated that we are able to detect GHB and GBL in a variety of containers including colourless and amber glass vials, plastic vials and polythene bags. We have also demonstrated the ability to detect both GBL and GHB in a range of liquid matrices simulating 'spiked' beverages.
Subject(s)
4-Butyrolactone/analysis , Beverages/analysis , Hydroxybutyrates/analysis , Spectrum Analysis, Raman/methods , Substance Abuse Detection/methods , Limit of DetectionABSTRACT
Knowledge and control of the polymorphic phases of chemical compounds are important aspects of drug development in the pharmaceutical industry. Salmeterol xinafoate, a long acting beta-adrenergic receptor agonist, exists in two polymorphic Forms, I and II. Raman and near infrared spectra were obtained of these polymorphs at selected wavelengths in the range of 488-1064 nm; significant differences in the Raman and near-infrared spectra were apparent and key spectral marker bands have been identified for the vibrational spectroscopic characterisation of the individual polymorphs which were also characterised with X ray diffractometry. The solid-state transition of salmeterol xinafoate polymorphs was studied using simultaneous in situ portable Raman spectroscopy and differential scanning calorimetry isothermally between transitions. This method assisted in the unambiguous characterisation of the two polymorphic forms by providing a simultaneous probe of both the thermal and vibrational data. The study demonstrates the value of a rapid in situ analysis of a drug polymorph which can be of potential value for at-line in-process control.
Subject(s)
Albuterol/analogs & derivatives , Calorimetry, Differential Scanning/methods , Spectrum Analysis, Raman/methods , Vibration , Albuterol/analysis , Albuterol/chemistry , Molecular Structure , Salmeterol Xinafoate , Spectrophotometry, Infrared , Temperature , X-Ray DiffractionABSTRACT
The Raman spectroscopic biosignatures of halotrophic cyanobacterial extremophiles from sabkha evaporitic saltpans are reported for the first time and ideas about the possible survival strategies in operation have been forthcoming. The biochemicals produced by the cyanobacteria which colonise the interfaces between large plates of clear selenitic gypsum, halite, and dolomitized calcium carbonates in the centre of the salt pans are identifiably different from those which are produced by benthic cyanobacterial mats colonising the surface of the salt pan edges in the intertidal zone. The prediction that similar geological formations would have been present on early Mars and which could now be underlying the highly peroxidised regolith on the surface of the planet has been confirmed by recent satellite observations from Mars orbit and by localised traverses by robotic surface rovers. The successful adoption of miniaturised Raman spectroscopic instrumentation as part of a scientific package for detection of extant life or biomolecular traces of extinct life on proposed future Mars missions will depend critically on interpretation of data from terrestrial Mars analogues such as sabkhas, of which the current study is an example.