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1.
Analyst ; 149(8): 2317-2327, 2024 Apr 15.
Artigo em Inglês | MEDLINE | ID: mdl-38466379

RESUMO

We investigate the subsurface composition of turbid materials at the micro scale by means of a portable non-invasive technique, micro-spatially offset Raman spectroscopy (micro-SORS), combined with shifted excitation Raman difference spectroscopy (SERDS). This combination enables the microscale layer analysis and allows to deal effectively with highly fluorescing samples as well as ambient light, all in a form of an in-house portable prototype device optimised for applications in heritage science. The instrument comprises ability to simultaneously collect multiple spectra by means of an optical fibre bundle, thus reducing the dead time and simplifying the ease of deployment of the technique. The performance of the synergy between micro-SORS and 785 nm SERDS dual-wavelength diode laser is demonstrated on a stratified mock-up painting samples including highly fluorescing painted layers. This instrumental approach could be ground-breaking in heritage science, due to the largely unmet need of analysing the molecular composition of subsurface of artworks non-invasively and in situ, and in the presence of fluorescent background and ambient light. Moreover, many other fields are expected to benefit from this technological advancement such as solar energy, forensic and food analytical areas.

2.
Cesk Slov Oftalmol ; 77(1): 45-48, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33740867

RESUMO

Orbital fractures may be accompanied with severe damage of the eye bulb and other intraorbital tissues. Early clinical findings can be very mild, therefore it is vital to actively seek not only for any damage done to the soft tissues of the orbit, but also for extraorbital complications such as liquorrhea or meningitis. We report a relatively rare case of blow-in fracture of orbital roof in eleven years old boy. Patient was admitted to the emergency care after falling off a bicycle without impaired consciousness. During admission ophthalmologist evaluated the condition as severe contusion of the left bulb, with hemophthalmia and retinal comotosis. Due to significant swelling of eye lids and periorbital hematoma, it was not possible to perform specific tests to objectify possible oculomotor disorder and diplopia. CT scan findings show dislocated fracture of orbital roof with fragments reaching into the musculus rectus superior. For high risk of bulbus penetration and muscle damage a surgical intervention with bone fragments removal was performed using endoscopic assisted frontal orbitotomy. After operation patient had no signs of functional eye disorder.


Assuntos
Órbita , Fraturas Orbitárias , Criança , Diplopia , Humanos , Masculino , Fraturas Orbitárias/diagnóstico , Fraturas Orbitárias/diagnóstico por imagem , Tomografia Computadorizada por Raios X
3.
Talanta ; 218: 121078, 2020 Oct 01.
Artigo em Inglês | MEDLINE | ID: mdl-32797864

RESUMO

This study proposes a non-invasive analytical method to study the molecular diffusion of a chemical agent into a turbid matrix with an emerging analytical technique, micro-Spatially Offset Raman Spectroscopy (micro-SORS). Here, the micro-SORS concept has been extended from the analysis of chemically distinct stratified layers to the studies and monitoring of the absorption and diffusion processes, addressing a key analytical need in a number of areas including polymer, pharmaceutical, forensic and biomedical sciences. In Cultural Heritage the knowledge of the penetration depth of a polymer used to consolidate or to protect an object, or the absorption depth of solvents used during a cleaning procedure is crucial for the performance evaluation of restoration methods and their safety towards the work of art. To date the most common protocol for obtaining this type of information comprises the application of stratigraphical analysis on cross-sections prepared after taking a small amount of sample from the work of art. This approach is destructive and may lack of statistical meaning, since the analytical information is limited to the micro area of sampling. To overcome these drawbacks, in this study micro-SORS was successfully used, for the first time, to non-invasively characterise the penetration of a polymer and of a viscous solvent into a gypsum substrate, permitting the reconstruction of the diffusion trends of the products into the matrix and the evaluation of their performances.

4.
Klin Onkol ; 30(4): 282-288, 2017.
Artigo em Tcheco | MEDLINE | ID: mdl-28832174

RESUMO

AIM: The aim of this study was to evaluate overall survival (OS) and prognostic factors in patients ineligible for chemotherapy who were treated with a hyperfractionated accelerated schedule with simultaneous integrated boost. MATERIAL AND METHODS: From May, 2008, to April, 2013, 122 patients with locally advanced nonmetastatic squamous laryngeal (14%), hypopharyngeal (30%), oropharyngeal (30%), and oral cavity (27%) cancer were treated at our institution. The median age, Karnofsky Performance Status (KPS), and gross tumor volume (GTV) of the patients were 63 years (range, 46-87 years), 80% (range, 50-100%), and 46 ml (range, 5-250 ml), resp. The median total dose of radiotherapy was 72.6 Gy (range, 62-77 Gy) at 1.4-1.5 Gy per fraction, and 55 Gy at 1.1 Gy per fraction was delivered for GTV (primary and lymphadenopathy) with a margin of 0.7 cm and regional lymphatic areas with a margin of 0.3 cm. The dose was delivered 2× a day, with a 6-8 hour interval between doses, via a 6 MeV linear accelerator. OS was estimated using the Kaplan-Meier method, and predictors of OS were analyzed using Cox proportional hazards regression. RESULTS: The median duration of the radiotherapy series was 37 days (range, 32-45 days). The incidence of grade 3 acute toxicity was 62% for mucosa (oral cavity and/or pharynx) and 0% for skin. Confluent mucositis cleared in all cases within 21 days. No grade 4 or 5 toxicities were recorded. PEG was introduced before treatment in 55 patients (45%). The 1-and 2-year OS was 65% and 32%, resp. KPS less than 80% (RR 2.4, 95% CI 1.3-4.2; p = 0.004), cancers other than oropharyngeal or laryngeal cancer (RR 2.0, 95% CI 1.1-3.5; p = 0.016), and capacity of high GTV (RR 1.006, 95% CI 1.001-1.011; p = 0.017) were found to be negative prognostic factors for OS. CONCLUSION: More than 30% of patients with poor prognosis survived for longer than 2 years. KPS before treatment was the strongest prognostic factor for better OS.Key words: head and neck cancer - radiotherapy dose fractionation - survival analysis - acceleration - hyperfractionation This work was supported by RVO-FNOs/2016 (HPV status as predictive and prognostic factor for primary and secondary head and neck cancer). The authors declare they have no potential conflicts of interest concerning drugs, products, or services used in the study. The Editorial Board declares that the manuscript met the ICMJE recommendation for biomedical papers.Submitted: 9. 3. 2017Accepted: 19. 4. 2017.


Assuntos
Fracionamento da Dose de Radiação , Neoplasias de Cabeça e Pescoço/mortalidade , Neoplasias de Cabeça e Pescoço/radioterapia , Radioterapia de Intensidade Modulada/métodos , Idoso , Idoso de 80 Anos ou mais , Neoplasias de Cabeça e Pescoço/patologia , Humanos , Estimativa de Kaplan-Meier , Pessoa de Meia-Idade , Prognóstico , Radioterapia de Intensidade Modulada/efeitos adversos , Resultado do Tratamento
5.
J Laryngol Otol ; 131(9): 779-784, 2017 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-28578716

RESUMO

OBJECTIVE: To identify deep neck infection factors related to life-threatening complications. METHODS: This retrospective multi-institutional study comprised 586 patients treated for deep neck infections between 2002 and 2012. The statistical significance of variables associated with life-threatening complications of deep neck infections was assessed. RESULTS: During treatment, life-threatening complications occurred in 60 out of 586 cases. On univariate analysis, life-threatening complications were linked to: dyspnoea, neck movement disturbance and dysphonia (all p < 0.001); and parapharyngeal, anterior visceral or pretracheal deep neck involvement (all p < 0.002). Aetiology was significantly linked to tonsils (p < 0.001). Regarding infection type, fasciitis was a significant factor (p < 0.001). Candida albicans was a significant bacterial culture (p < 0.001). A multivariate step-wise model disclosed fewer significant variables: retropharyngeal space (p = 0.005) and major blood vessels area (p = 0.006) involvement, and bacterial culture C albicans (p < 0.001). CONCLUSION: It can be predicted that patients with deep neck infections, with neck movement disturbances, dysphonia, dyspnoea and swelling of the external neck, accompanied by severe pain, and inflammatory changes in the retropharyngeal space and large vessel areas, with culture-confirmed infection of C albicans, are likely to develop life-threatening complications.


Assuntos
Infecções Bacterianas/classificação , Infecções Bacterianas/mortalidade , Pescoço/microbiologia , Adulto , Idoso , Idoso de 80 Anos ou mais , Infecções Bacterianas/microbiologia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Modelos Teóricos , Estudos Retrospectivos , Índice de Gravidade de Doença , Análise de Sobrevida , Adulto Jovem
6.
Clin Otolaryngol ; 42(3): 597-601, 2017 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-27759910

RESUMO

OBJECTIVE: The human papillomavirus (HPV) causes recurrent respiratory papillomatosis (RRP). Although HPV prevalence is high, the incidence of papillomatosis is low. Thus, factors other than HPV infection probably contribute to RRP. This study investigated whether patients with papillomatosis are more often infected with herpes simplex virus type 2 and chlamydia trachomatis (ChT) and whether laryngopharyngeal reflux (LPR) occurs in this group of patients more often. DESIGN: Prospective case-control study. SETTING: Department of Otorhinolaryngology of University Hospital. PARTICIPANTS: The study included 20 patients with adult-onset RRP and 20 adult patients with vocal cord cyst and no pathology of laryngeal mucosa (control group). MAIN OUTCOME MEASURES: Immunohistochemical analysis of pepsin, HPV, herpes simplex virus type 2 and ChT was performed in biopsy specimens of laryngeal papillomas and of healthy laryngeal mucosa (control group) obtained from medial part of removed vocal cord cyst during microlaryngoscopy procedures. RESULTS: Pathologic LPR (pepsin in tissue) was diagnosed in 8/20 (40.0%) patients with papillomatosis and in 0/20 control patients (P = .003). Herpes simplex virus type 2 was present in 9/20 (45.0%) patients with papillomatosis and in 0/20 control patients (P = .001). Five specimens were positive for both pepsin and herpes simplex virus type 2. No samples were positive for ChT. There were no significant differences between groups for age, body mass index, diabetes mellitus and gastrooesophageal reflux disease. Tobacco exposure was not more frequent in RRP group either (P = .01). CONCLUSIONS: Results show that LPR and herpes simplex virus type 2 are significantly more often present in patients with RRP. LPR and herpes simplex virus type 2 might activate latent HPV infection and thereby be possible risk factors for RRP.


Assuntos
Herpes Simples/complicações , Herpesvirus Humano 2/imunologia , Refluxo Laringofaríngeo/complicações , Papillomaviridae/imunologia , Infecções por Papillomavirus/etiologia , Infecções Respiratórias/etiologia , Adulto , Idoso , Idoso de 80 Anos ou mais , Anticorpos Antivirais/análise , Estudos de Casos e Controles , República Tcheca/epidemiologia , Herpes Simples/epidemiologia , Humanos , Incidência , Refluxo Laringofaríngeo/epidemiologia , Pessoa de Meia-Idade , Infecções por Papillomavirus/epidemiologia , Prevalência , Estudos Prospectivos , Infecções Respiratórias/epidemiologia , Fatores de Risco , Adulto Jovem
7.
Cesk Slov Oftalmol ; 72(5): 178-181, 2016.
Artigo em Tcheco | MEDLINE | ID: mdl-28224803

RESUMO

PURPOSE: To compare the success rate of monocanalicular (MI) and bicanalicular intubation (BI) in congenital nasolacrimal duct obstruction (CNLDO). METHODS: MI through the inferior canaliculus and BI were performed under general anaesthesia in children from 7 to 24 months old with CNLDO. Only children after unsuccessful conservative therapy and two and more probings were included in the study. The tubes were removed 3 months after intubation and the therapeutic success was evaluated 6 months after intubation. RESULTS: There were performed 139 MI in 114 children and 119 BI in 88 children. The success rate 6 months after intubation is 135/139 (97.1%) in MI, 114/119 (95.8%) in BI and the difference in therapeutic results between MI and BI is not significant (p = 0.737). CONCLUSION: Silicone intubation is an effective procedure for treating CNLDO without difference in therapeutic success between MI and BI.Key words: congenital nasolacrimal duct obstruction (CNLDO), monocanalicular intubation (MI), bicanalicular intubation (BI).


Assuntos
Intubação/métodos , Obstrução dos Ductos Lacrimais/congênito , Obstrução dos Ductos Lacrimais/terapia , Ducto Nasolacrimal/cirurgia , Stents , Pré-Escolar , Tratamento Conservador , Feminino , Humanos , Lactente , Masculino , Ducto Nasolacrimal/anormalidades , Silicones , Resultado do Tratamento
8.
Analyst ; 141(3): 731-9, 2016 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-26646435

RESUMO

This article reviews a very recent field of noninvasive analysis of turbid media using micro-scale Spatially Offset Raman Spectroscopy - micro-SORS. The technique combines conventional SORS with microscopy concepts and represents a new imaging modality in Raman microscopy. Micro-SORS facilitates analytical capability for investigating non-destructively the chemical composition of subsurface, micrometer-scale-thick diffusely scattering layers at depths more than an order of magnitude larger than those accessible with the depth resolving power of conventional confocal Raman microscopy. Potential application areas include nondestructive subsurface analysis of painted layers in cultural heritage, characterization of stratified polymer systems, analysis of layered biological samples or forensic analysis. The article discusses the basic principles of the technique, its variants and outlines emerging applications in this rapidly evolving field.


Assuntos
Análise Espectral Raman/métodos , Método de Monte Carlo , Pintura/análise , Papel , Espalhamento de Radiação , Sementes/química , Triticum
9.
Analyst ; 140(24): 8127-33, 2015 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-26526114

RESUMO

We compare several basic embodiments of a recently proposed and demonstrated micrometer-scale Spatially Offset Raman Spectroscopy (micro-SORS). Micro-SORS is a recently introduced analytical method for noninvasive characterisation of the chemical composition of subsurface, micrometre-scale-thick diffusely scattering layers at depths beyond the reach of conventional confocal Raman microscopy. The technique is applicable, for example, in nondestructive subsurface analysis of highly scattering stratified matrices such as painted layers in cultural heritage or in noninvasive analysis of stratified polymer systems or biological samples. Using Monte Carlo simulations, we analysed two defocusing variants of micro-SORS and a variant involving a full separation of illumination and collection zones on the sample surface. Both the penetration depth into the sample and relative enhancement of sublayer Raman signals were studied as a function of layer thickness and type of technique and their parameters. The model predicts that the most effective method by far is the variant with fully spatially separated illumination and collection zones. On the other hand, the defocusing micro-SORS, where both the laser and Raman collection zones are defocussed and overlapped, yielded the lowest performance although its key benefit lies in its simplicity as the concept can be practiced on existing conventional Raman microscopes without any modifications. A basic experimental verification of the theoretical findings contrasting two extreme modalities, the fully separated micro-SORS variant with the defocusing one, is also presented.


Assuntos
Análise Espectral Raman , Microscopia Confocal , Método de Monte Carlo
10.
Aust Dent J ; 60(2): 212-5, 2015 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-25988277

RESUMO

BACKGROUND: The aim of this study was to review the bacteriology of deep neck infections (DNI) and identify the factors that influence the incidence of causative bacteria. METHODS: A retrospective analysis of 634 patients with DNI was performed. Statistical analysis was used to compare the incidence of common pathogens in various conditions such as age of the patients, aetiology and associated diabetes mellitus. RESULTS: Bacteria were isolated in 514 cultures (81%). Aerobic bacteria were isolated from 246 cultures (39%) and anaerobic bacteria from 61 cultures (10%). Both aerobic and anaerobic bacteria were isolated from 207 cultures (32%). The most common aerobic bacteria were Streptococcus pyogenes (41%) and Staphylococcus aureus (32%). The most common anaerobic bacteria were Peptostreptococcus species (28%), followed by Prevotela species (8%) and Proprionibacterium species (7%). The incidence of anaerobic bacteria was higher in adults, in patients with infections of dental origin and in non-diabetic patients. CONCLUSIONS: The bacteriology of DNI is polymicrobial, including both aerobic and anaerobic bacteria. The incidence of anaerobic bacteria is higher in adults, in patients with infections of dental origin and in non-diabetic patients.


Assuntos
Abscesso/epidemiologia , Diabetes Mellitus , Pescoço , Staphylococcus aureus/isolamento & purificação , Streptococcus pyogenes/isolamento & purificação , Abscesso/microbiologia , Abscesso/prevenção & controle , Adolescente , Adulto , Fatores Etários , Idoso , Idoso de 80 Anos ou mais , Bactérias Aeróbias/isolamento & purificação , Bactérias Anaeróbias/isolamento & purificação , Criança , Pré-Escolar , República Tcheca/epidemiologia , Feminino , Humanos , Incidência , Lactente , Masculino , Pessoa de Meia-Idade , Estudos Retrospectivos , Fatores de Risco , Infecções Estafilocócicas/epidemiologia , Infecções Estafilocócicas/microbiologia , Infecções Estafilocócicas/prevenção & controle , Infecções Estreptocócicas/epidemiologia , Infecções Estreptocócicas/microbiologia , Infecções Estreptocócicas/prevenção & controle , Adulto Jovem
11.
Cesk Slov Oftalmol ; 68(5): 202-6, 2012 Nov.
Artigo em Tcheco | MEDLINE | ID: mdl-23461372

RESUMO

OBJECTIVES: To determine the role of transnasal endoscopic approach to orbital lesions. METHODS: Retrospective case series. RESULTS: Three patients underwent endoscopic diagnostic surgery for orbital lesions. In all three patients was successfully finded out the diagnosis, the orbita was decompressed. In two cases it resulted to visual recovery, in one case was determine a diagnosis of metastatic adenocarcinoma. In one case the tumor was removed totally. CONCLUSION: Using endoscopic approach to the orbit allowed good approach to the biopsy of orbital lesions, allowed decompression an in limited count of cases this access allowed a complete tumour removal. On the other hand, generally endoscopic approach is useful only for limited lesions (extraconal), usually it allowed only debunking, not the complete resection of orbital pathology.


Assuntos
Endoscopia/métodos , Procedimentos Cirúrgicos Oftalmológicos/métodos , Neoplasias Orbitárias/cirurgia , Adulto , Feminino , Humanos , Masculino , Pessoa de Meia-Idade
12.
Rhinology ; 49(3): 375-80, 2011 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-21858272

RESUMO

PURPOSE: To determine the success rate of revision endoscopic dacryocystorhinostomies (DCR) and to analyse 44 revision DCRs. METHODS: The operative and postoperative data were collected in 44 revision DCRs. The corrections of associated structural anatomic alterations were performed during the surgery (resection of the scarr, the bone window creating, resection of the head of the middle turbinate, septoplasty, ethmoidectomy etc.) and the intubation was performed in all cases. RESULTS: The follow-up interval ranged from 12 to 36 months. The 44 ReEDCRs were performed in adults and there were only 5 children under the age of 15. The surgery was performed under local or general anaesthesia. The most frequent secondary procedures were scar resections, creating a wider bone window, and partial middle turbinate resection. Four patients were excluded for their follow-up periods had not been completed. An average time of the tubes removal was 5.6 months. The total success rate was 84.0%; the success rate was 85.7% in the group with closed rhinostomy and 1/2 in the group of canalicular and rhinostomy obstructions. CONCLUSIONS: The endonasal revision DCR is a safe and very effective surgical procedure following the failed DCRs. The correction of associated structural anatomic alterations that may be involved in the failure of previous surgeries can be easily performed.


Assuntos
Dacriocistorinostomia/métodos , Adolescente , Idoso de 80 Anos ou mais , Criança , Endoscopia , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Reoperação , Estudos Retrospectivos , Resultado do Tratamento , Adulto Jovem
13.
Opt Lett ; 33(20): 2386-8, 2008 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-18923631

RESUMO

A short-pulse source based on optical parametric chirped-pulse amplification (OPCPA) technology has been developed with properties that make it a suitable seed for a high-energy OPCPA system. This source generated a diffraction-limited pulse at 910 nm with a full bandwidth of > 165 nm and a spectrum having a transform-limited pulse duration of less than 15 fs. The technique has potential for generating bandwidths > 200 nm and pulse durations < 10 fs.

14.
Anal Chem ; 80(21): 8146-52, 2008 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-18785759

RESUMO

We demonstrate experimentally the feasibility of monitoring the depth of optically thick layers within turbid media using spatially offset Raman spectroscopy (SORS) in combination with multivariate analysis. The method uses the deep penetration capability of SORS to characterize significantly thicker (by at least a factor of 2) layers than possible with conventional Raman spectroscopy. Typical relative accuracies were between 5 and 10%. The incorporation of depth information into a SORS experiment as an additional dimension allows pure spectra of each individual layer to be resolved using three-dimensional multivariate techniques (parallel factor analysis, PARAFAC) to accuracies comparable with the results of a two-dimensional analysis.


Assuntos
Nefelometria e Turbidimetria/instrumentação , Nefelometria e Turbidimetria/métodos , Análise Espectral Raman/instrumentação , Análise Espectral Raman/métodos
15.
Cesk Slov Oftalmol ; 64(3): 91-4, 2008 May.
Artigo em Tcheco | MEDLINE | ID: mdl-18630157

RESUMO

In patients with bilateral symptoms of lacrimal pathways occlusion, the endonasal dacryocystorhinostomy (EDCR) and conjunctivo-dacryocystorhinostomy (CDCR) may be performed simultaneously or consequently. The simultaneous bilateral surgery does not worsen the surgery results. The advantages of this procedure are one anesthesia only, only unsubstantial extension of the surgery duration, and shorter sick leave as well. The authors performed during the period from 1995 to 2007 altogether 630 primary EDCRes and 117 CDCRes. In 92 patients, 184 simultaneous dacryocystorhinostomies were performed. Out of 164 evaluated surgeries, the good results were obtained in 150 cases (91.5 %). Out of 40 simultaneously performed CDCRes (20 patients), they were successful in 14 patients. Unsuccessful they were in 3 patients in whom the silicone drainage implant was used.


Assuntos
Túnica Conjuntiva/cirurgia , Dacriocistorinostomia , Adolescente , Adulto , Idoso , Idoso de 80 Anos ou mais , Criança , Pré-Escolar , Humanos , Pessoa de Meia-Idade
16.
Anal Chim Acta ; 607(1): 50-3, 2008 Jan 21.
Artigo em Inglês | MEDLINE | ID: mdl-18155409

RESUMO

We demonstrate the potential of Raman spectroscopy to detect cocaine concealed inside transparent glass bottles containing alcoholic beverages. A clear Raman signature of cocaine with good signal-to-noise was obtained from a approximately 300 g solution of adulterated cocaine (purity 75%) in a 0.7 L authentic brown bottle of rum with 1 s acquisition time. The detection limit was estimated to be of the order of 9 g of pure cocaine per 0.7 L (approximately 0.04 moles L(-1)) with 1 s acquisition time. The technique holds great promise for the fast, non-invasive, detection of concealed illicit compounds inside beverages using portable Raman instruments, thus permitting drug trafficking to be combated more effectively.


Assuntos
Bebidas Alcoólicas/análise , Cocaína/análise , Análise Espectral Raman/métodos , Detecção do Abuso de Substâncias/métodos , Cocaína/química , Etanol/química , Drogas Ilícitas/análise , Drogas Ilícitas/química
17.
Appl Spectrosc ; 61(10): 1123-7, 2007 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-17958964

RESUMO

A simple procedure for the recovery of deep subsurface Raman spectra in stratified turbid samples by defocusing a conventional Raman instrument is presented. The method is based on effects present with spatially offset Raman spectroscopy (SORS) and, although not as efficient as the standard SORS approach, it permits a simple way of recovering subsurface Raman spectra from less challenging samples. Demonstration of the effect is performed using a standard SORS device and a commercial Raman instrument on the noninvasive measurement of paracetamol tablets held within a nontransparent white plastic bottle.


Assuntos
Coloides/química , Misturas Complexas/química , Nefelometria e Turbidimetria/instrumentação , Nefelometria e Turbidimetria/métodos , Análise Espectral Raman/instrumentação , Análise Espectral Raman/métodos , Desenho de Equipamento , Análise de Falha de Equipamento , Reprodutibilidade dos Testes , Sensibilidade e Especificidade
18.
Anal Chem ; 79(21): 8185-9, 2007 Nov 01.
Artigo em Inglês | MEDLINE | ID: mdl-17880183

RESUMO

We present a Raman spectroscopic method for the noninvasive detection of liquid explosives within bottles, and other packaging, of substantially higher sensitivity and wider applicability than that currently available via conventional Raman spectroscopy. The approach uses a modification of the spatially offset Raman spectroscopy (SORS) concept, which permits the interrogation of a wide range of containers, including transparent, colored, and diffusely scattering plastic and glass beverage, medicine, and cosmetic bottles, with no change in experimental geometry. The enhanced sensitivity is achieved by the technique's inherent ability to effectively suppress fluorescence and Raman contributions originating from the wall of the container. The application is demonstrated on the noninvasive detection of hydrogen peroxide solution, a critical component of a number of liquid explosives. In contrast to conventional Raman spectroscopy, the modified SORS concept enables the detection of concealed hydrogen peroxide solution in all the studied cases.

19.
Photochem Photobiol Sci ; 6(9): 987-94, 2007 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-17721598

RESUMO

Time-resolved infrared absorption spectra of the C[triple bond]N bands of photoexcited TMABN and DMABN have been measured in non-polar hexane, polar aprotic THF and polar protic butanol with high temporal and spectral resolution (<0.5 ps and 5 cm(-1), respectively). In butanol, the intramolecular charge transfer (ICT) state C[triple bond]N infrared absorption bands of DMABN and TMABN both develop from an initial singlet into a doublet, demonstrating the co-existence of two charge transfer excited states, one of which is hydrogen-bonded and the other similar to the state formed in aprotic solvents. The ICT C[triple bond]N absorption band of TMABN is already strong at the earliest measurement time of 2 ps in THF, hexane, and butanol, indicating prompt population of ICT by a barrierless process, as expected from the pre-twisted structure of this molecule. There are little or no subsequent fast kinetics in hexane and THF but the signal observed in butanol continues to grow substantially at later times, prior to decay, indicating population transfer from a second state excited at 267 nm. No CN absorption band attributable to this state is observed, consistent with it being similar to the LE state of DMABN. The kinetics of the later stages of the hydrogen-bonding of both DMABN and TMABN in butanol takes place on timescales consistent with known values for dipolar solvation relaxation and result in a ratio of the hydrogen-bonded to non-bonded species of approximately 3 : 1 at equilibrium for both molecules. The contrast between the prompt population of the charge transfer state of TMABN in all three solvents and charge transfer rates in DMABN limited to 13 ps(-1) in THF and 9 ps(-1) in butanol is fully consistent with the TICT description for the ICT state structure.

20.
Appl Spectrosc ; 61(8): 845-54, 2007 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-17716403

RESUMO

A new, passive method for enhancing spontaneous Raman signals for the spectroscopic investigation of turbid media is presented. The main areas to benefit are transmission Raman and spatially offset Raman spectroscopy approaches for deep probing of turbid media. The enhancement, which is typically several fold, is achieved using a multilayer dielectric optical element, such as a bandpass filter, placed within the laser beam over the sample. This element prevents loss of the photons that re-emerge from the medium at the critical point where the laser beam enters the sample, the point where major photon loss occurs. This leads to a substantial increase of the coupling of laser radiation into the sample and consequently an enhanced laser photon-medium interaction process. The method utilizes the angular dependence of dielectric optical elements on impacting photon direction with its transmission spectral profile shifting to the blue with increase in the deviation of photons away from normal incidence. This feature enables it to act as a unidirectional mirror passing a semi-collimated laser beam through unhindered from one side, and at the other side, reflecting photons emerging from the sample at random directions back into it with no restrictions to the detected Raman signal. With substantial restrictions to the spectral range, the concept can also be applied to conventional backscattering Raman spectroscopy. The use of additional reflective elements around the sample to enhance the Raman signal further is also discussed. The increased signal strength yields higher signal quality, a feature important in many applications. Potential uses include sensitive noninvasive disease diagnosis in vivo, security screening, and quality control of pharmaceutical products. The concept is also applicable in an analogous manner to other types of analytical methods such as fluorescence or near-infrared (NIR) absorption spectroscopy of turbid media or it can be used to enhance the effectiveness of the coupling of laser radiation into tissue in applications such as photodynamic therapy for cancer treatment.

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